Strong, soft, tear resistant insulating compositions and composites for extreme cold weather use

ABSTRACT

Novel gels and gel composites for direct contact with the body and capable of substantially preventing the generation moisture from said body in extreme cold weather use.

RELATED APPLICATIONS AND PATENTS

This application is a continuation-in-part application of copendingapplications entitled: “Novel Crystal Gels Useful as Dental Floss WithImproved High Tear, High Tensile, and Resistance to High Stress RuptureProperties”, filed Sep. 30, 1997; Ser. No. 08/581,125 filed Dec. 29,1995, now U.S. Pat. No. 5,962,572; Ser. No. 08/581,188 filed Dec. 29,1995, now abandoned; Ser. No. 08/909,487 filed Aug. 12, 1997, U.S. Pat.No. 6,050,871; Ser. No. 08/581,191, Dec. 29, 1995 now U.S. Pat. No.5,760,117; Ser. No. 08/845,809 filed Apr. 29, 1997, now U.S. Pat. No.5,938,439; Ser. No. 08/863,794 filed May 27, 1997; Ser. No. 08/819,675filed Mar. 17, 1997 now U.S. Pat. No. 5,884,639; Ser. No. 08/719,817filed Sep. 30, 1996; Ser. No. 08/665,343 filed Jun. 17, 1996, Ser. No.08/612,586 filed Mar. 8, 1996; PCT/US/94/07314 filed Jun. 27, 1994,PCT/US94,04278, filed Apr. 19, 1994; Ser. No. 08/288,690 filed Aug. 11,1994 now U.S. Pat. No. 5,633,280. The subject matter contained in therelated application and patents are specifically incorporated herein byreference.

FIELD OF THE INVENTION

The present invention relates to novel gel compositions, gel composites,articles, and method of making same.

BACKGROUND OF THE INVENTION

Nine mountain climbers died on Mt. Everest this year. Those that made itback to their Himalayan base camp and lifted out of danger (byhelicopter) lost toes, fingers, nose and body tissue damaged byfrontbite. The foot of the climbers were well protected. Each climberhad don on at least two pairs of socks, a boot liner, an inner boot andan outer boot for insulation against the elements. Even with suchprotection, frostbite can occur. Skin protection against the cold is aconcern not only of mountain climbers to the highest peak of the world,but also of great concern to military strategist planing trainingmaneuvers in the Arctic and Antarctic environments, to scientist workingin cold regions of the world, to radar workers manning equipment inSiberia and North Dakota, to sports enthusiast (skiers, hunters, sleddog racers, etc.) and to people living everyday lives in the Arctic andAntarctic regions. NASA is concern with protecting man in the coldenvironments of deep space. The Navy is concern with ways to protect manin the cold water environments below the ice surface. The Army has itsCold Region Research Environment Laboratory and one of its mission is toevaluated materials and fabric for protecting the human body againstcold.

One of the most advanced cold weather boots available is fitted with ashell, a layer of thermal insole, a moisture trap layer with a top layerof foam insulation surrounding the feet. Body heat is trapped in (a) awarm air insulation matrix surrounding the foot surface, followed by (b)a high moisture vapor transfer (high air permeability lining fabric,over a (c) high efficiency foam insulation, (d) a high moisture vaportransfer and low air permeability outer fabric, and (e) a shell fabricwhich deflects the wind and stabilizes the insulating air. Anotherequally advanced cold weather boot is described in U.S. Pat. No.:4,845,862.

Up to the present time, cold weather boots are not capable of preventingfrostbite of the foot. The causes of frostbite are poor bloodcirculation cause by the compaction of foot and compacted foot moisturelatent insulating materials. The compacted insulating material alsoallows for rapid conduction of heat away from the foot by the presenceof excessive moisture. In some cold weather boots, foot moisture isallowed to collect and freeze directly below the foot insulating layer.Once foot moisture the collects and freezes, it can form a conductingpath for heat to leave the boot. Frostbite results when the foot isallowed to remain in prolong extreme cold conditions. Unless themoisture latent socks and any frozen moisture inside the boot and belowthe insulating layer are removed and the foot is kept warmed and dried,the water in the foot is in danger of freezing into crystals of ice. Theneed to protect the foot also applies to the other parts of the humanskin that may be exposed to the cold, such as the face, the neck, thefingers, the nose, the ears, and other parts of the body.

U.S. Pat. No. 3,660,849 discloses a insulative deep submergence divingsuit based on a flexible supporting surface layer substantially fullycovering a very low modulus gel of SIS and SBS block copolymer-mineraloil and glass microbubble filler. The problem with such a gel suit madefrom a SIS and SBS is that the suit can easy break apart, rip, or tearunder its own weight without the flexible support. The flexible supportcovering the inside surface of the suitable also isolates the gel.

SUMMARY OF THE INVENTION

I have unexpectedly discovered insulating elastic gel compositions,insulating gel composites, and insulating gel articles for protectingthe skin of the human body from cold, which acts as a body insulator.Parts of the skin which can e advantageously protected by the insulatinggels and gel composites of the invention include the face, the fingers,the hand, the nose, the ears, the foot and the like. The insulating gelsand gel composite are of advantage for forming articles for the humanbody exposed to extreme cold environments such as encountered inmountain climbing, in outer space, in the deep oceans, and beneath thebelow zero waters and on wind swept lands 60° north and south latitudesencompassing the polar regions of the Arctic and Antarctic circles.

The insulating elastic gels, insulating gel composites, and insulatinggel articles of the invention composes: (i) one or more layers of thesame or different insulating elastic gels, having one or more integralhomogeneous or inhomogeneous insulating components disposed in said gelin combination with or without (ii) one or more layers of elastic gelsor one or more gel composite layers, wherein (i) or (ii) with or without(iii) one or more layers of a fabric, a polymeric open cell foam or apolymeric closed cell foam; wherein (i), (ii), or (iii) in combinationwith or without (iv) one or more hydrophilic moisture absorbing andretaining layers or patches between said insulating elastic gel layerand skin, said elastic gel layer, or said composite gel layer and one ormore layers of a fabric or a polymeric open cell foam; said insulatinggel and composite gel being in direct selected contact with the skin andcapable of substantially preventing the skin from generating moisture.Moreover, the insulating gel and insulating gel composites are highlytear resistant, fatigue resistant, soft and strong and advantageouslyuseful in direct gel contact with the skin protecting it from extremecold.

DESCRIPTION OF THE DRAWINGS

FIGS. 1-14b. Illustrate embodiments of insulating gels and insulatinggel composites.

FIGS. 15-19. Illustrate embodiments of insulating gels and insulatinggel composites in cross-sectional views of foot wear.

FIG. 20. View of thumb finger representing the hand.

FIGS. 21-22. View of thumb finger representing the hand withcross-sectional of insulating gel and insulating gel composite gloves.

FIG. 23. View of the human head.

FIGS. 24-28. Illustrate embodiments of the human head with insulatinggel and insulating gel composite head-face-neck masks.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

With respect to the Drawings: FIGS. 1-14B, we adopt the followingconvention: For example, the composite of FIG. 1 is denoted byG_(n)(G_(n)M_(m))M_(n)M_(n), a composite. The composite“G_(n)(G_(n)M_(m))M_(n)M_(n)” comprises a G_(n) layer laminated to a“(G_(n)M_(m))” layer. The (G_(n)M_(n)) layer with the “( . . . )”denotes a gel composition of M_(m) that is dispersed in G_(n). Next, the(G_(n)M_(m)) layer is laminated to a M_(n) layer which is laminated toanother M_(n) layer. When the subscript m is the subscript of M, mdenotes the same or a different dispersion material. When n is asubscript of M, n is the same or different selected from the groupconsisting of paper, foam, plastic, concrete, fabric, metal, concrete,wood, glass, ceramics, synthetic resin, synthetic fibers or refractorymaterials. Where n is the subscript of G_(n), n denotes the same or adifferent gel G with the same or a different rigidity.

Thus by convention, (G_(n)M_(m)), denotes a gel G_(n) with a homogeneousor non-homogeneous dispersion of a material M_(m). As another example,FIG. 7 is denoted by M_(n)(G_(n)M_(m))M_(n)M_(n), FIG. 9 is denoted byM_(n)(G_(n)M_(m))M_(n), FIG. 10B is denoted by M_(n)G_(n)M_(n), FIG. 11is denoted by G_(n)M_(n), FIG. 13 is denoted by G_(n)M_(n)G_(n)M_(n),FIG. 14B is denoted by G_(n)M_(n)G_(n), and the like.

Body moisture, and especially forehead, neck, underarm, and footmoisture are a problem in extreme cold weather. Up to now, cold weatherboots have been designed not only to insulate the foot, but to allowfoot moisture vapor to be collect and trap beneath the foot in amoisture trap layer between the insulating layer and the insole where itis easily frozen and remains frozen at subfreezing temperatures. Withpart of the shoe between the insulating layer and the insole frozen,heat can escape the boot more readily by way of the frozen layer insidethe boot. There are various patents related to foot moisture management(U.S. Pat. No. 4,898,007), foot moisture control (U.S. Pat. No.5,095,548), moisture management sock and shoe for creating a moisturemanaging environment for the feet (U.S. Pat. Nos. 5,319,807 and5,353,524) and footwear for facilitating the removal and dissipation ofperspiration from the foot of a wearer (U.S. Pat. Nos. 5,365,677 and5,511,323). Such are of little or no help when prolong exposure toextreme cold occurs.

In extreme cold environments, foot moisture can be detrimental and evenfatal causing frostbite of the toes and foot. It's every difficult towalk on frozen feet. A person whose foot is frostbitten would be lesslikely to reach a place of safety or be able to survive very coldweather conditions.

The present invention takes a completely different direction from thedesign and function of the prior art. The insulating gels of the coldweather wear (FIGS. 15-28) such as boots, face mask, gloves, full bodywear, and the like have as an essential, direct contact with the skin ofthe body. The present invention is directed to cold weather body wearsuch as boots, face mask, gloves, and full body wear (for work or play)capable of substantially preventing, controlling or selectivelyfacilitating the production of moisture from selected parts of the skinof the body such as the forehead, neck, foot, underarm, etc.

With respect to the footwear of my invention, it is advantageouslyuseful for protecting the skin of the foot from frostbite in extremecold weather. This is accomplished in four ways; thermally insulatingthe barefoot, providing a non-compacting material for non-constrictingblood flow in the foot by dissipating impact and shock to the foot, andreduce or substantially eliminate or prevent the production of footmoisture by the barefoot. The barefoot, for example, can be protectedadvantageously from extreme cold by using the insulating gel orinsulating gel composites (FIGS. 1-14b) of the invention. The footwearof my invention for protecting the skin of the foot in cold weathercomprises: (I) an outer boot (16); (II) one or more dimensionally stablesubstantially hydrophobic insulation gel sock (15) (FIG. 15) or a gelcomposite sock (18) (FIGS. 16-19) impregnated with one or moredimensional stable substantially hydrophobic insulating gels disposed insaid boot and formed of a material and in sufficient amounts capable ofremovably encapsulating and integrally in sealing contact with the skinof the foot and one or more toes of the foot so as to substantiallydisplace the air surrounding the skin of the foot and substantiallyprevent the production of moisture from the axis of said foot, and

(III) a thermal insulation member (17) disposed between said gel sock(15) or gel composite sock (18) and said boot; said gel is a elasticgel, a non-plastic gel, a solid gel, a foamed gel, an open cell gel, ora closed cell gel; said gel in combination with or without one or moreantiperspirant agents, deodorant agents, antibacterial agents,antifungal agents, and hydrophobic agents; said gel being capable ofallowing equal distribution of font pressure and non-constriction ofblood circulation in the foot.

The footwear comprises a outer boot (14) with or without a rigidstructural member to provide for vertical stability about the ankleareas. The outer boot can be made from any suitable boot material.Depending on the nature of the activity, the outer boot (16) can be madefrom any man made or natural strong, tough, flexible water repellentmaterial, including plastics, hydrophobic treated leathers, natural orman made rubbers, thermoplastic elastomers, hydrophobic treated fabrics,metals, silicone rubbers, polyurethane elastomers, other water repellentstrong, tough, flexible polymeric materials, or a combination thereof.Material suitable for forming the outer boot include polyethylene,polyethylene copolymers, polypropylene, polypropylene copolymers, highimpact polystyrene, polystyrene copolymers, polyvinlychloride,polyurethane, polybutylene, polycarbonate, polyester, polyimide,polyvinylidene chloride, acrylonitrile compolymers, and the like.

In addition to the outer boot, a thermal insulation member (17) isdisposed inside the boot. The thermal insulation member inside of theboot comprises one or more thermally insulating material layers. Theinsulating material layers can be one or more layers of any suitableneutral or man made thermally insulating materials including: close cellfoams, open cells foams, materials containing insulating particles(microspheres), natural hairs, natural and synthetic wools, cotton, andthe like. The thickness of the insulating member (17) layered materialscan be less than 1 cm to 3 cm or greater depending on the degree ofinsulation required.

Between the barefoot and the insulating member (17) layers, the foot issurrounded by one or more dimensionally stable substantially hydrophobicthermally insulating gel (15) sock or a gel composite sock (18, 23, 22).The gel composite sock is formed from any suitable material, M_(n),impregnated with one or more dimensional stable substantiallyhydrophobic thermally insulating gels, G_(n). The gel sock (15) or gelcomposite (18, 23, 22) sock is disposed is the boot for receiving andsurrounding the barefoot and formed of a material and in sufficientamounts capable of removably encapsulating and integrally in sealingcontact with the skin of the foot and one or more toes of the foot so asto substantially displace the air surrounding the barefoot andsubstantially prevent the production of moisture from the skin of saidfoot. The gel, G_(n), where n denotes a elastic gel, a non-elastic gel,a solid gel, a foamed gel, an open cell gel, or a closed cell gel, saidgel in combination with or without one or more antiperspirant agents,deodorant agents, antibacterial agents, antifungal agents, andhydrophobic agents; said gel being capable of allowing equaldistribution of foot pressure and non-constriction of blood circulationin the foot. The gel, G_(n), can be a silicone gel, a urethane gel, athermoplastic elastomer gel or a combination thereof. Such gels arecapable of “wetting” the surface of the skin so as to prevent thegeneration of body moisture. Of greatest advantage is the use ofselected thermoplastic elastomer gels which are tear resistant andfatigue resistant. The gel can be made additionally more insulating byincorporating open cell voids of closed cell voids (man mademicrospheres) forming a gel foam (22) sock having reduced weight. In thecase of open cell gels, the gel on the inside of the boot facing theskin surface is made to have a thick continuous, un-broken gel surfaceso as to prevent air from contacting the skin of the foot.

The gels mentioned herein which are of advantage are strong, tearresistant, fatigue resistant, soft, pliable, and capable of removablyencapsulating and in sealing contact with the skin of the foot so as tosubstantially displace the air surrounding the skin surface of the footand prevent air from contacting the skin of the foot.

For most purposes, such as boots for walking on level polar ice orfrozen tundra in the Arctic, on level Antarctic terrain, or on the leveldeck of an ice breaker, a thin layer of gel (15) is adequate theencapsulate and seal the skin of the foot from air and prevent theproduction of foot moisture. In the case of active sports, such as a skiboots or hunting boots, a gel laminated (18) sock is disposed in theboot with the gel side encapsulating and sealing the skin of the footfrom air and prevent the production of foot moisture.

For the average climbing boots, a multi-interwoven layered sock isdisposed in the boot. The inner top layers of the interwoven,multi-layered sock is impregnated with sufficient amounts of gel (25) soas to form a stable support and sufficient for encapsulating and sealingthe skin of the foot from air and prevent the production of fontmoisture. In the case of rugged mountain climbing boots that requires ahighly more stable boot inner support, the top few millimeter of surfaceof a natural or synthetic dense batting material, a dense open cellfoam, or a felt material can be use to form the bottom of the inner gel(26) sock disposed in the hoot. The top layer of the inner sock surfaceis impregnated with gel (24) forming a highly stable support and capableof encapsulating and sealing the skin of the foot from air and preventthe production of foot moisture. In all cases, sufficient gel is presentin the areas under, over and between the toss to insulate and provide asealing contact of the gel with the skin in and about the toe region toencapsulate and seal the skin surrounding the toes from air and preventthe production of foot moisture.

As contemplates, (15) is G_(n) or the composite of FIG. 11. The gelcomposite layers denoted by (18), (23), (24), and (26) are illustratedby FIGS. 1-3, 8-14 b. The composite (22) is illustrated by FIGS. 8-10A,and 11-14 a.

Moreover, the gel sock or gel composite sock for receiving andsurrounding the foot can be further separated from the insulating layerby a barrier, such as a polymeric membrane or file keeping one or morecomponents of the gel or agents from migrating into the insulatinglayer.

In general, the boot, the outer boot shell, the boot ankle supportjoint, the sole, the insulating layer, and gel sock are designed to takeinto account the gait cycle. The subtalar or heel joint allows the footto dissipate the forces generated while walking. The positions of theheel while walking are supination, neutral, pronation, returning toneutral and then to the supination position. In part, the gel and gelcomposites will help greatly dissipate the force generated by walking.Walking in extreme cold ice or snow weather conditions can be very slow.

Likewise, the hands and fingers can be protected against frostbite byusing insulating gel and insulating gel composite lined gloves (FIGS.20-22). The face is also protected by using insulating gels and gelcomposites forming the head, face, and neck masks (FIGS. 23-28). Thecomposites of FIGS. 1-14b are of advantage for protecting the head, faceand neck. Perforations (FIGS. 24-28) can be form in the gel or gelcomposite insulating layers at the regions of the nose, mouth, and ear.Oxygen breathing connections (13) can be formed as an integral part ofthe insulting mask (FIG. 24). Inner water absorbent patches can beinserted through slits at (11) at the forehead, neck, (of the mask) andother parts of the body in a gel composite body suite such as at theunderarm regions and torso, back, arms (not shown in the drawings). Thepatches can be easy inserted and removal through the slits as desired.The patches can be placed selectively almost anywhere about the bodywhile the reminder parts of the body are prevented from generating bodymoisture. The hydrophilic patches can be made from any moistureadsorbing material capable of absorbing at least 50% of its weight ofwater. Such hydrophilic materials include, natural materials (cotton) orwater absorbing polymers, hydrogen forming polymers, said tolerant superabsorbent (U.S. Pat. No. 5,274,018), starch modified adsorbents (U.S.Pat. No. 4,103,062 and 3,938,522), polysaccharide (starch or cellulosemodified polymers). These and other water absorbing materials such asdisclosed in U.S. Pat. Nos. 5,599,335; 5,536,264, 5,532,350, 5,505,718,5,422,169, 5,419,956, 5,39,626, 5,330,822, 5,180,622, 5,149,334,5,147,343, 5,143,680, 4,921,904, 4,892,533, 4,824,901, 4,813,945,4,755,178, 4,755,562, 4,605,401, 4,429,001, 4,366,294, 3,788,872, andthe like are herein incorporated by reference. The hydrophilic patchesare held in place by the gel on one side and in direct contact with theskin. In the case where direct contact of the patches to the skin is notdesirable, the patches or hydrophilic materials can be place in slitpockets between the gel or gel composite layer and a foam pocket orfabric pocket layer facing the skin. The gel or gel composite pocketlayers of advantage for inserting the hydrophilic patches include gellayer-pocket-foam layer, gel or gel composite layer-pocket-fabric layer.The pockets for receiving the hydrophilic patches are formed by placingout blanks of the shape and size of the intended patches between the geland form or gel and fabric layers before laminating. After thelamination is complete, one or more slits are out from the gel layerside to remove the cut blanks. The slit cuts are made overlapping theblanks so that when the patches are inserted, the slits are on theoverlapped portion of the patches. The side of the patches facing awayfrom the skin can also be coated with a gel to provide for insulatingsealing at the slits when inserted into the pockets.

In the eye area, correction lens (FIG. 25) or wide view visor (FIGS.26-28) can be incorporated as a tri-layer of M_(n)G_(n)M_(n) (FIG. 10b)or G_(n)M_(n)G_(n) (FIG. 14b). The visor layers include polystyrenelayer/gel layer/polystyrene layer, polycarbonate layer/gellayer/polycarbonate layer, crystalline polypropylene layer/gellayer/polypropylene layer, clear silicone layer/gel layer/siliconelayer, and the like.

The (G_(n)M_(m)), (M_(n) dispersed in G_(n)), layer is made from a lowconcentration to a high concentration of insulating microspheres. As forpurpose of distinction, the low to moderate concentration ofmicrospheres in the gel is referred to insulating gels. The highlyconcentrated microsphere containing gels also have the attribute ofbeing fluffy and light. There are also referred to as fluffy, light,soft, airy compositions. The high concentration dispersion Fluffy,light, soft, airy, solid, strong elastic gelatinous elastomercomposition, (G_(n)M_(m)), exhibiting substantially complete resistanceto elastic deformation, capable of substantial complete shape memoryrecovery and being dimensionally stable, wherein when n is a subscriptof G, n denotes the same or a different gel rigidity. The gel of theinvention is formed from (I) 100 parts by weight of at least one or morehigh viscosity block copolymer; (II) about 300 to about 1,600 parts byweight of a plasticizing oil; and in combination with or without (IV)and (V) described below. The fluffy, elastic solid gelatinous elastomercomposition, (G_(n)M_(n)), is made from (I), (II), and (III) a selectedamount of one or more heat expandable plastic or synthetic particulatematerial dispersed in an ordered, random, homogeneous, nonhomogeneous,stratified, partially stratified or one or more separated phases and incombination with or without (IV) and (V) described below. The dispersedparticulate material is capable of producing a predetermined volume ofclosed cell particulate dispersion forming said (G_(n)M_(n)) having adensity of from about 0.80 g/cm³ to less than about 0.60 g/cm³, a gelrigidity of from about 20 to about 3,000 gram Bloom, and an elongationof at least 200%.

The G_(n) and M_(n) can be in adhering contact, laminated or physicallyinterlocked with a selected material M_(n) to form a compositecomprising combinations of G_(n) and M_(n) any sequential additions orpermutations of said combinations G_(n)G_(n), M_(n)G_(n),G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), M_(n)M_(n)G_(n),M_(n)G_(n)G_(n)G_(n), M_(n)M_(n)M_(n)G_(n), includingM_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n), G_(n)G_(n)M_(n)G_(n),M_(n)G_(n)M_(n)M_(n), M_(n)G_(n)M_(n)G_(n), G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)M_(n), G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n)G_(n), G_(n)G_(n)G_(n)M_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n), M_(n)G_(n)M_(n)G_(n)M_(n),G_(n)G_(n)M_(n)M_(n)M_(n), G_(n)M_(n)M_(n)G_(n)M_(n),G_(n)G_(n)G_(n)M_(n)G_(n)G_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)M_(n)G_(n)M_(n)G_(n)M_(n), G_(n)M_(n)M_(n)G_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n)M_(n), G_(n)G_(n)M_(n)M_(n)G_(n)G_(n),M_(n)M_(n)G_(n)G_(n)M_(n)M_(n), M_(n)G_(n)G_(n)M_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n)G_(n)G_(n)H_(n),G_(n)M_(n)G_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),M_(n)G_(n)M_(n)G_(n)M_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n)M_(n)M_(n)G_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n),G_(n)G_(n)M_(n)M_(n)G_(n)G_(n)M_(n)M_(n),G_(n)G_(n)M_(n)G_(n)G_(n)M_(n)G_(n)G_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)G_(n),G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)or combinations thereof.

The (G_(n)M_(m)) can be in adhering contact, laminated or physicallyinterlocked with a selected G_(n), (G_(n),M_(m)) or material M_(n) toform a composite comprising combination of (G_(n)M_(m)) any sequentialadditions or permutations of said combinations of (G_(n)M_(m)),(G_(n)M_(m)))G_(n)M_(m)), (G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m)),M_(n)M_(n)(G_(n)M_(m)), M_(n)G_(n)G_(n)(G_(n)M_(m)),M_(n)M_(n)M_(n)(G_(n)M_(m)), including M_(n)G_(n)(G_(n)M_(m)),(G_(n)M_(m))G_(n)M_(n), G_(n)(G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m))M_(n),M_(n)(G_(n)M_(m))G_(n), (G_(n)M_(m))G_(n)G_(n), (G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)M_(n), (G_(n)M_(m))G_(n)M_(m)M_(n),(G_(n)M_(m))G_(n)M_(n)G_(n), (G_(n)M_(m))M_(n)G_(n)G_(n),G_(n)G_(n)(G_(n)M_(m))M_(n), M_(n)G_(n)(G_(n)M_(m))G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m)), G_(n)(G_(n)M_(m))M_(n)M_(n),(G_(n)M_(m))M_(n)(G_(n)M_(m)), G_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n), G_(n)(G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m)),(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)),G_(n)(G_(n)M_(m))M_(n)G_(n)G_(n), M_(n)M_(n)G_(n)(G_(n)M_(m))M_(n),M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), (G_(n)M_(m))(G_(n)M_(m))G_(n),M_(n)M_(n)M_(n)(G_(n)M_(m))M_(n)M_(n),M_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),M_(n)(G_(n)M_(m))(G_(n)M_(m))M_(n)G_(n),(G_(n)M_(m))M_(n)(G_(n)M_(m))M_(n)G_(n),M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m))M_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m)),(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n)G_(n), or(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n).

The (I) block copolymer component(s) forming the G_(n) of the inventionis a linear, multi-arm, branched, or star shaped copolymer of thegeneral configuration poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-styrene), poly(styrene-butylene-styrene),poly(styrene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-styrene),poly(styrene-ethylene-ethylene/butylene-butylene-styrene),poly(styrene-butylene-ethylene/propylene-butylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-styrene),poly(styrene-ethylene-butylene-ethylene/butylene-styrene),poly(styrene-ethylene-butylene-ethylene/propylene-styrene),poly(styrene-ethylene/butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-butylene-ethylene/butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene/propylene-butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/butylene-butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene),poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylene-butylene-styrene),poly(styrene-ethylene-butylene), poly(styrene-ethylene-propylene)_(n),poly(styrene-ethylene)_(n), poly(styrene-butylene)_(n),poly(styrene-ethylene-ethylene/butylene)_(n),poly(styrene-ethylene-ethylene/propylene),poly(styrene-butylene-ethylene/propylene)_(n),poly(styrene-butylene-ethylene/butylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene)_(n),poly(styrene-ethylene-ethylene/butylene-butylene)_(n),poly(styrene-butylene-ethylene/propylene-butylene)_(n),poly(styrene-butylene-ethylene/butylene-butylene)_(n),poly(styrene-ethylene-butylene-ethylene/butylene)_(n),poly(styrene-ethylene-butylene-ethylene/propylene)_(n),poly(styrene-ethylene/butylene-ethylene/propylene)_(n),poly(styrene-ethylene-ethylene/butylene-ethylene/propylene)_(n),poly(styrene-ethylene-ethylene/propylene/-ethylene/butylene)_(n),poly(styrene-butylene-ethylene/butylene-ethylene/propylene)_(n),poly(styrene-butylene-ethylene/propylene-ethylene/butylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)_(n),poly(styrene-ethylene/propylene-butylene-ethylene/propylene)_(n),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene)_(n),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene)_(n),poly(styrene-ethylene-ethylene-butylene-butylene-ethylene/propylene)_(n),poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene)_(n),poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)_(n),poly(styrene--ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene)_(n),poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylenebutylene)_(n) or a mixture thereof. The G_(n) can also be made with orwithout a (IV) selected amount of at least one polar polymer selectedfrom the group consisting of ethylene-butylene acrylate, ethylene-ethylacrylate, ethylene-methyl acrylate, ethylene-vinyl acetate,ethylene-vinyl acrylate, ethylene-vinyl alcohol,acrylonitrile-styrene-acrylate, styrene-acrylonitrile, styrene-maleicanhydride, meleated poly(styrene-ethylene-propylene-styrene) or meleatedpoly(styrene-ethylene-butylene-styrene); and in combination with orwithout a (V) selected amount of at least one crystalline ornon-crystalline polymer or copolymer selected from the group consistingof poly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene), low viscositypoly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), meleatedpoly(styrene-ethylene-butylene-styrene), high vinyl contentpoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene-ethylene-propylene),poly(ethylene-propylene), poly(styrene-butadiene)_(n),poly(styrene-butadiene)n, poly(styrene-isoprene)_(n),poly(styrene-isoprene)_(n), poly(styrene-ethylene-propylene)_(n), lowviscosity poly(styrene-isoprene)_(n), poly(styrene-isoprene)_(n), lowviscosity poly(styrene-ethylene-butylene)_(n),poly(styrene-ethylene-butylene)_(n), meleatedpoly(styrene-ethylene-butylene)_(n), high vinyl contentpoly(styrene-ethylene-butylene)_(n),poly(styrene-ethylene-propylene-styrene-ethylene-propylene)_(n),poly(ethylene-propylene)_(n), polystyrene, polybutylene,poly(ethylene-propylene), poly(ethylene-butylene), polypropylene,polyethylene, or polypthalamide, wherein said selected block copolymeris a linear, branched, multiarm, or star shaped copolymer.

As used herein, the term “gel rigidity” in gram Bloom is determined bythe gram weight required to depress a gel a distance of 4 mm with apiston having a cross-sectional area of 1 square centimeter at 23° C.

It is found that for the block copolymer gels described herein,including insulating gels, insulating gel composition, and fluffy gels,the tensile strength and tear strength are essentially independentproperties. For any particular gel, it can exhibit high tensilestrength, but weak tear strength, likewise, a gel can exhibit high tearstrength, but low tensil strength. The best tensile and tear strengthgels are those having greater crystallinity and elasticity. The tensileof all block copolymer gels including the crystalline gels can beimproved by the addition of (1-15% weight) crystalline andseim-crystalline (V) polymers, such as additions of higher density andhigher molecular weight (higher melt index) polyethylene andpolypropylene. The tear strength can be improved by additions (1-15%weight) of branched, multiblock, radial, star bock copolymers (with atleast 20% weight and block content), polyethylene copolymers,polypropylene copolymers, thermoplastic polyurethane elastomers,polyphenylene oxide, high molecular weight polystyrene, polycarbonate,and the like. Hence, for example 1-10% weight of polypropylene and 1-10%weight of poly(dimethylphenylene)oxide can further improve the tensileand tear strength of the gels of the invention. Likewise combinations ofthe other polymers described can provide a balanced of better tensile,better tear and better fatigue resistant gel properties. The highertensile and tear properties can be compared to that of a Kraton G1651 orSEPTON 8006 (SEBS) and Kraton GRP 6918 or SEPTON 2006 (SEPS) gels havingthe same rubber to plasticizer ratio, but without the substantial blockcopolymer crystallinity and tensile and tear improving polymercomponents. In all cases, the pure (SEBS) and (SEPS) gels exhibit lowertensile, lower tear, and lower fatigue properties.

The various types of high viscosity linear, branched, multiarm, or starshaped block copolymers employed as one or more component(s) forming theinsulating gels, C_(n) as well as the gel component for the fluffy,strong, solid shape recoverable elastic gelatinous elastomercomposition, (G_(n)M_(n)), of the invention are of the generalconfigurations A-Z-A and (A-Z)_(n), wherein the subscript n is two more(e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, etc). In the case of multiarm blockcopolymers where n is 2, the block copolymer denoted by (A-Z)_(n) is thelinear block copolymer A-Z-A, for sake of simplicity the stable couplingagent residue is ignored.

The end block segment (A) comprises a glassy amorphous polymer and blocksegment, preferably polystyrene and the midblocks (2) comprises amidblock of poly(ethylene), poly(butylene), poly(ethylene-butylene),poly(ethylene-propylene) or a combination thereof.

Advantageously, G_(n) can be made substantially more tear resistant,more resistant to high shear and high stress rupturing by selectingblock copolymers with one or more substantially crystallinepoly(ethylene) midblock (simply denoted by “-E- or (E)”) in combinationwith one or more amorphous midblocks of poly(butylene),poly(ethylene-butylene), poly(ethylene-propylene) or combination thereof(the amorphous midblocks are denoted by “-B- or (B)”, “-EB- or (EB)”,and “-EP- or (EP)” respectively or simply denoted by “-W- or (W)” (whenreferring to one or more of the amorphous midblocks as a group) not tobe confused with (Z) which denotes the midblocks (-E-, -EB-, -B-, -EP-and -W-) between the end (A) blocks. The A and Z portions areincompatible and form a two or more-phase system consisting ofsub-micron amorphous glassy domains (A) interconnected by (Z) chains.The glassy domains serve to crosslink and reinforce the structure. Thisphysical elastomeric network structure is reversible, and heating thepolymer above the softening point of the glassy domains temporarilydisrupt the structure, which can be restored by lowering thetemperature.

The G_(n) of the invention having one or more block copolymers withsubstantially crystalline polyethylene midblocks are hereafter referredto as “fluffy elastic-crystalline gels” or simpler “fluffy crystalgels”. The block midblocks of copolymers forming the fluffy crystal gelsare characterized by sufficient crystallinity as to exhibit a meltingendotherm of at least about 40° C. as determined by DSC curve. Thefluffy, elastic solid gelatinous elastomer composition of the inventionmade from block copolymers having substantially no crystallinepolyethylene midblocks are hereafter referred to as “fluffyelastic-amorphous gels” or simpler “fluffy amorphous gels”. Forsimplicity, the fluffy amorphous gels and fluffy crystal gels will bereferred to generally as “fluffy gels” or even more simply as G_(n)above. When referring to the gels' amorphous or crystal nature, theywill be referred to as fluffy amorphous gels and fluffy crystal gels.

More surprisingly and advantageously, certain selected unique fluffycrystal gels of the invention have the unique ability to exhibit timedelay complete elastic-recovery from its extended or deformed state orshape back to its original state and shape. This is attributed the blockcopolymer component(s) having a higher crystalline -E- segmentmidblock(s).

The amorphous block copolymer components are advantageously modified bythe presence of the higher crystalline -E- segment(s) which may resistcrazing and cavitation that immediately precedes fibrillation of thepolystyrene domains due to applied stress causing catastrophic crackdevelopment and failure of the fluffy gels without adequate crystalline-E- segments.

The fluffy gels can be made in combination with a selected amount of oneor more (IV) and/or (V) polymers and copolymers including thermoplasticcrystalline polyurethane elastomers with hydrocarbon blocks,homopolymers, copolymers, block copolymers, polyethylene copolymers,polypropylene, polypropylene copolymers, and the like described below.

The high viscosity linear (I) block copolymers are characterized ashaving a Brookfield Viscosity value at 5 weight percent solids solutionin toluene at 30° C. of from at least about 35 cps to about 60 cps andhigher, advantageously from about 40 cps to about 160 cps and higher,more advantageously from about 50 cps to about 180 cps and higher, stillmore advantageously from about 70 cps to about 210 cps and higher, andeven more advantageously from about 90 cps to about 380 cps and higher.

The high viscosity (I) branched, star-shaped or multiarm blockcopolymers are characterized as having a Brookfield Viscosity value at 5weight percent solids solution in toluene at 30° C. of from about 80 cpsto about 380 cps and higher, advantageously from about 150 cps to about260 cps and higher, more advantageously from about 200 cps to about 580cps and higher, and still more advantageously from about 100 cps toabout 800 cps and higher.

The high viscosity linear (I) high vinyl content SEBS block copolymersare characterized as having a Brookfield Viscosity value at 10 weightpercent solids solution in toluene at 25° C. of from at least about 35cps to about 100 cps and higher, advantageously from about 40 cps toabout 80 cps and higher, more advantageously from about 50 cps to about70 cps and higher, still more advantageously from about 50 cps to about90 cps and higher, and even more advantageously from about 60 cps toabout 100 cps and higher.

Using Toluene Viscosity at 10% solids at 25° C. of approximately 1,800cP or the equivalent viscosity at 5 weight percent solids solution intoluene at 30° C. of approximate 40 as reference for the linear blockcopolymer SEBS (Kraton G 1651), the various ranges considered as highviscosities denoted above for the different block copolymers (linear,multiarm, radial, an branched block copolymers) although somewhatdifferent are substantially comparable in molecular weights.

The various aspects and advantages of the invention will become apparentto those skilled in the art upon consideration of the accompanyingdisclosure and the drawings.

Extremely Light fluffy, strong, and highly elastic gel compositions areunknown in the art. The solid fluffy gels employed in the presentinvention are different and not the same as the visco-elastic fluids ormaterials of patents '913 and '657. The gels of the instant invention donot exhibit the property of the visco-elastic fluids and are notflowable in the ambient state, but remains substantially a elastic solidbelow its “A” domain's a glassy disassociation temperature or meltingpoint. In order to make strong, dimensionally stable, solid elasticoil-gels from high viscosity block copolymers, it is necessary toprocess the oil and high viscosity block copolymers at high temperaturesabove about 150° C. to about 200° For sufficient long times until ahomogeneous molten blend is obtained. Such oil-gels can also be madeusing high intensity mixers for about 50 minutes at 190° C.-210° C.under vacuum. Under such process conditions, the molten oil and blockcopolymer gel viscosities can be quite high depending on the rate ofshear. At even low shear rates, the molten block copolymer gel exhibitviscosities greatest at above about the glassy domain melting point.Even above the glassy domain melting point, the melt viscosities can bevery high. As an example, the viscosity at 5% concentration in oil at300° F. for a high viscosity poly(styrene-ethylene-butylene-styrene)block copolymer can be as high as 42,700 cps. At about slightly belowthe processing temperature, the molten high viscosity block copolymergel becomes a weak solid. At about 300° F., the gel exhibit thecharacter of a weak elastic solid. O course, at ambient temperature, itis impossible to even incorporate a single microsphere into the gel,because the gel is solid. Consequently, incorporating even a small ormoderate amount of microspheres into the molten gel at processingtemperatures is difficult. It would only further greatly increase themolten gel's viscosity making it more difficult to process. The increaseviscosity with each addition of microspheres makes for an impossibletask to obtain a truly light weight fluffy elastic gel. Microspheressuch as those made from methacrylonitrile can be easily and quicklydestroyed under such long times at high process temperatures and shearabove its rupture temperature T_(max). Incorporation of sufficientamount of methacrylonitrile microspheres to make a light fluffy “closescell” elastic solid gel is heretofore unrealized and unobtainable.Incorporation of even a small amounts of unexpanded methacrylonitrilemicrospheres is impossible due to the high molten gel viscosity andtemperature conditions. Upon exposure of the unexpanded microspheres tosuch high process temperature, the microspheres instantly expands andbecame even more difficult to work into the molten gel due to themicrosphere's increased size, low density in combination with theextreme high molten gel viscosity and high pressure temperatures.

Consequently, adding unexpanded thermoplastic microspheres such asmethacrylonitrile microspheres at or near its upper temperature limitsT_(max), will only increase the already high viscosity of the moltenoil-block copolymer gel.

The prior art ('657) did not recoGnize the relationship of hightemperature, high molten viscosity and high block copolymerconcentrations, the prior art would have had no motivation to solve thehigh molten viscosity problem at the high temperature processconditions; it is apparent the prior art avoided the problem by notadding any microspheres (expanded or unexpanded) at such high processingtemperatures (1) by reducing the block copolymer concentration (therebylowering the viscosity of the oil and block copolymer composition, and(2) by lowering the temperature of the polymer-oil mixture to ambientbefore adding any microspheres. Therefore the fluffy gels of the instantinvention are not inherent in the process or the composite microsphereand lubricant mixture taught by U.S. Pat. No. 5,626,657. Clearly,heating of unexpanded thermoplastic microspheres such asmethacrylonitrile microspheres at such high temperatures in a high blockcopolymer content/oil mixture is not taught by the prior art.

Therefore, a method I found to make a strong, fluffy, elastic solid gelhaving a density of at least less than 0.6 g/cm³ is totally unexpected.

Expanded methacrylonitrile microspheres are not advantageous and can notbe fully utilized to make the fully gels of the invention at therequired high process temperatures; while, unexpanded methacrylonitrilemicrospheres will explode up to almost 50 times their volume (very muchline “pop corn”) when exposed to above their T_(start) temperatures. Thetemperature at which they start expanding or popping, however, are toolow (106-135° C.) to be suitable for incorporation into the highviscosity molten gel at the needed gel processing temperatures. Theadvantage of using unexpanded microspheres is that they can be veryeffective for making rapid expansive foams below their T_(max) expansiontemperatures provided they do not rupture. Hence, their low T_(max)temperature prevent their use for foaming at the high block copolymerconcentrations and high gel processing temperatures. Therefore, the lowtemperature properties of the unexpanded microspheres and the processconditions of the molten gel makes it impossible to make fluffy gelsbefore the present invention.

The problem is to find ways to enable the unexpanded microspheres to be(i) added and dispersed in substantial quantities in the molten gelwithout substantially increasing the gel's molten viscosity. (ii) delayor retard the start of their expansion in the molten gel to allow forsufficient dispersion, (iii) limit, restrict or control their exposurethe high rupture (T_(max)) temperatures while being dispersed in themolten gel, and (iv) adequately allowing dispersion of the microspheresparticles into the molten gel.

Conventionally, in order to low the molten gel viscosity to provide forsufficient dispersion of the microspheres, the process temperaturesneeds to be increased which pushes the process temperature even higherabove the microsphere's rupture temperature. Whereas, attempting tomaintain a sufficient low process temperature (at or below T_(max)) andapplying high pressures will require high shear resulting uncontrollablepressure and viscosity fluctuations which will result in inadequatedispersion.

A simple solution to the critical conditions i-iv has been found toprovide fluffy gels having a density of at least less than about 0.6g/cm³, more advantageously at least about 0.5 g/cm3, still moreadvantageously at least about 0.4 g/cm3, and still more advantageouslyat least about 0.3 g/cm3 or less.

Not only are fluffy gels obtained, gels which are fluffy as well asstrong, highly elastic, exhibit shape-memory, resistant to tear, highshear and high stress rupturing, and exhibit controlled delay responseand slow, complete recovery from extension and deformation are alsoobtained.

I have now discovered a method of incorporating large quantities ofunexpanded microspheres, delay the microspheres' onset of expansion bycontrolling their exposure to high heat, thereby, allowing adequatelytime to disperse the microspheres particles into the molten gel. Themethod I found is as follows:

As a first approximation, I determine the time required for adequatelymixing a selected volume or mass of molten gel as a function oftemperature and molten gel viscosity. This allows for a betterunderstanding of the mixing equipment and conditions chosen for makingthe fluffy gels of the invention. This can be determined for any largeor medium mixing equipment used, even a small test tube.

The components I, II, IV and V of the invention blend easily in the meltand a heated vessel equipped with a stirrer is all that is required.While conventional large vessels with pressure and/or vacuum means canbe utilized in forming large batches of the instant fluffy crystal gelsin amounts of about 40 lbs or less to 10,000 lbs or more. For example,in a large vessel, inert gases can be employed for removing thecomposition from a closed vessel at the end of mixing and a partialvacuum can be applied to remove any entrapped bubbles. Stirring ratesutilized for large batches can range from about less than 10 rpm toabout 40 rpm or higher).

Simply mix a selected, predetermined amount of ingredients I and II inthe chosen equipment under heat (at a constant rate of mixing) at thelowest temperature that will provide a homogeneous clear, optionallytransparent molten gel mixture. Add a selected amount of color (e.g.,orange color) polypropylene pellets and measure the time required touniformly disperse the color pellets in the molten gel. Next, increasethe temperature to decrease the molten gel viscosity and add a hand fullof a different colored high density polypropylene pellets and measurethe time required to uniformly dispersed the second colored pellets inthe molten gel. Repeat the procedure to obtain atime-temperature-viscosity relationship graph of the time required touniformly mix a selected volume or mass at increasing temperatures andvarying viscosities of the molten gel in the chosen equipment. By thismethod, the time, t_(u), required to uniformly disperse a units volumeor mass in the molten gel at any selected temperature or viscosity canbe determined.

In making a fluffy gel, I need to (1) predetermine the rigidity andquantity of the final fluffy gel I with to make, (2) estimate the finalprocess temperature and viscosity before incorporating the unexpandedmicrospheres into the hot molten gel, (3) combine selected raw materials(I) and/or (IV) and (V) ingredients, and (4) add a predeterminedselected amount of (II) ingredient, (5) blend together the components asdesired at about 23° C. to about 100° C. forming a paste like mixtureand further heating said mixture uniformly to about 150° C. to about200° C. until a homogeneous molten blend is obtained (Lower and highertemperatures can also be utilized depending on the viscosity of the oilsand amounts of block copolymers and polymer used.

With the predetermined amount of the remainder (II) ingredient, I (6)add and mix with it a selected measured quantity of (III) unexpandedmicrospheres at ambient temperature. The predetermined amount of (II)ingredient utilized initially to make the molten gel can range betweenless than about 75% to about 95% or higher (according to the criteriaset out below). Depending on the final molten gel temperature,viscosity, and volume or quantity of the preselected molten gel, I setthe following general guide and requirements: match the viscosity of themixture of (II) and (III) to form a (IIIa) (unexpanded microsphere/oil)mixture with a viscosity (4 b) about as close as possible matching theviscosity of the molten gel. I then estimate and select a time, t_(u),for mixing a unit volume of the molten gel from the graph (temperature,time, viscosity and equipment relationship). Then I determined bymeasuring in a preheated oven (set at the same temperature as thetemperature of the molten gel) the time, t_(r), required to raise thetemperature of the mass of (IIIa) from ambient to the temperatureT_(max). I then adjust t_(r) by adding from the remainder ingredient(II) additional amounts to (IIIa) until the time (t_(r)) equalspreferably at least about {fraction (1/20)}(t_(u)), more preferably{fraction (1/10)}(t_(u)), still more preferably about at least ¼(t_(u)),and especially more preferably about at least ½(t_(u)). When the moltengel temperature is below T_(max), the t_(r) selected chosen ispreferably from about less than {fraction (1/10)}(t_(u)) to about¼(t_(u)) or higher. When the molten gel temperature is above t_(max),the t_(r) selected is preferably from about less than about ¼(t_(u)) toabout ½(t_(u)) or higher. The reason for increasing the mass of IIIa isto prevent the temperature surrounding the microspheres to rise tooquickly in the higher temperature molten gel. Hence, the greater thent_(u) or added mass selected, the lower the viscosity and longer thetime available for adequate dispersion of the unexpanded microspheres inthe molten gel.

Following the criteria above, a fluffy gel can be obtained of almost anydesired density. The polymers forming the gels of the invention aredescribed and illustrate in copending application No. 863,794 andincorporated herein by reference. Theory notwithstanding, the blockcopolymer structures can be spheroid, cylinders, plates, and orderedbicontinuous are also within the scope of the present invention.Cylinder and plate structure are obtained with increasing glassy a endblocks. From about 15-30% by weight of A blocks, the block copolymerstructure is spheroid. From about 30 about 40% by weight of A blocks,the block copolymer structure becomes cylindrical for linear blockcopolymers and ordered bicontinuous structures (OBDD) for multi-armblock copolymers; and above about 45% A blocks, the structure becomesless cylindrical and more plate like for linear block copolymers andabout 60% and higher the structure becomes OBDD for linear blockscopolymers as well.

The advantages of sufficient crystalline —E— block copolymer midblocksegments for improving gel tear and stress rupturing is unknown in theart. For example, U.S. Pat. No. 5,132,355 teaches gelling liquidhydrocarbons by polyethylene block copolymers to yield pumpablehydrocarbon polymer mixtures containing a gelling polyethylene blockcopolymer agent. U.S. Pat. No. 5,276,100 disclose solid block copolymershaving improved resistance to clod flow. Other patents such as U.S. Pat.Nos. 5,571,864 and 5,654,364 are directed to miscible polyolefin blendswith modifying polyolefin having matching segment lengths and miscibleblend of polyolefin and polyolefin block copolymer. These patents areincorporated herein by reference.

Block copolymers containing high butylene midblock segments orsubstantially equal segment lengths of ethylene and butylene or ethyleneand propylene are highly amorphous and are suitable for making fluffyamorphous gels of the invention, but such fluffy gels are generallyweaker (with respect to tear, stress, rupture, and fatigue resistance)than crystal gels of the invention.

In order to obtain fluffy elastic crystal gels, however, it is necessarythat the selective synthesis of butadiene produce sufficient amounts of1,4 poly(butadiene) that on hydrogenation can exhibit “crystallinity” inthe midblocks. In order for the block copolymers forming the fluffycrystal gels of the invention to exhibit crystallinity, the crystallinemidblock segments must contain long runs of —CH₂— groups. There shouldbe approximately at least 16 units of —(CH₂)— in sequence forcrystallinity. Only the (—CH₂—)₄ units can crystallize, and then only ifthere are at least 4 units of (—CH₂—)₄ in sequence; alternatively, thepolyethylene units are denoted by [—CH₂—CH₂—CH₂—CH₂)-]₄, [(—CH₂—)₄]⁴ or(—CH₂—)¹⁶. The amount of (—CH2)—)¹⁶ units forming the (E) midblocks ofthe block copolymers comprising the fluffy crystal gels of the inventionshould be at least about 20% which amount is capable of exhibiting amelting endotherm in differential scanning calorimeter (DSC) curves.

Advantageously, the elastomer midblock segment should have acrystallinity of at least about 20% of (—CH₂—)16 units of the total mole% forming the midblocks of the block copolymer, more advantageously atleast about 25%, still more advantageously at least about 30%,especially advantageously at least about 40% and especially moreadvantageously at least about 50% and higher. Broadly, the crystallinityof the midblocks should range from at least about 20% to about 60%, lessbroadly from at least about 18% to about 65%, and still less broadlyfrom at least 22% to about 70%.

The melting endotherm in DSC curves of the crystalline block copolymerscomprising at least 20% crystallinity are much higher than conventionalamorphous block copolymers. The maximum in the endotherm curves of thecrystalline block copolymers occurs at about 40° C., but can range fromgreater than about 25° C. to about 60° C. and higher. The crystallineblock copolymers forming the fluffy crystal gels of the invention canexhibit melting endotherms (as shown by DSC) of about 25° C. to about75° C. and higher. More specific melting endotherm values of thecrystalline midblock block copolymers include: about 28° C., 29° C., 30°C., 31° C., 32° C., 33° C., 34° C., 35° C., 36° C., 37° C., 38° C., 39°C., 40° C., 41° C., 42° C., 43° C., 44° C., 45° C., 46° C., 47° C., 48°C., 49° C., 50° C., 51° C., 52° C., 53° C., 54° C., 55° C., 56° C., 57°C., 58° C., 59° C., 60° C., 61° C., 62° C., 63° C., 64° C., 65° C., 66°C., 67° C., 68° C., 69° C., 70° C., 71° C., 72° C., 73° C., 74° C., 75°C., 76° C., 77° C., 78° C., 79° C., 80° C., 90° C., 100° C., 110° C.,120° C., and higher, whereas, the melting endotherm (DSC) forconventional amorphous midblock segment block copolymers are about 10°C. and lower.

The melting endotherm is seen on heating and a sharp crystallizationexotherm is seen on cooling. Such midblock crystallization endothermicand exothermic characteristics are missing from DSC curves of amorphousgels. The crystallization exotherm and fusion endortherm of thecrystalline block copolymer gels of the invention are determined by ASTMD 3417 method.

Generally, the method of obtaining long runs of crystalline —(CH₂)— isby sequential block copolymer synthesis followed by hydrogenation. Theattainment of fluffy crystal gels of the instant invention is solely dueto the selective polymerization of the butadiene monomer (forming themidblocks) resulting in one or more predetermined amount of 1,4poly(butadiene) blocks followed by sequential polymerization ofadditional midblocks and hydrogenation to produce one or morecrystalline midblocks of the final block copolymers.

The crystalline block copolymers are made by sequential block copolymersynthesis, the percentage of crystallinity of (—CH₂—)¹⁶ units should beat least about (0.67)⁴ or about 20% and actual crystallinity of about12%. For example, a selectively synthesized S—EB_(n)—S copolymer havinga ratio of 33:67 of 1,2 and 1,4 poly(butadiene) on hydrogenation willresult in a midblock with a crystallinity of (0.67)⁴ or 20%. For sake ofsimplicity, when n is a subscript of —EB—, n denotes the percentage of(—CH2—)₄ units, eg, n=33 or 20% crystallinity which is the percentage of(0.67)⁴ or “(—CH₂—)₁₆” units. Thus, when n=28 or 72% of (—CH₂—)₄ units,the % crystallinity is (0.72)⁴ or 26.87% crystallinity attributed to(—CH₂—)₁₆ units, denoted by —EB₂₈—. As a matter of convention, and forpurposes of this specification involving hydrogenated polybutadiene: thenotation —E— denotes at least about 85% of (—CH₂)13 )₄ units. Thenotation —B— denotes at least about 70% of [—CH₂—CH(C₂H₅)—] units. Thenotation —EB— denotes between about 15 and 70% [—CH₂—CH(C₂H₅)—] units.The notation —EB_(n)— denotes n% [—CH₂—CH(C₂H₅)—] units. Forhydrogenated polyisopropene: The notation —EP— denotes about at least90% [—CH₂—CH(CH₃)—CH₂—CH₂—] units.

Likewise, in order to obtain the highly amorphous midblock componentssuch as —B— forming the fluffy amorphous gels, it is necessary that theselective synthesis of butadiene produce sufficient amounts of vinyl or1,2 poly(butadiene) that on hydrogenation can exhibit “substantiallyamorphous polybutene” midblocks. The notation —B— denotes greater thanabove about 70% [—CH2—CH(C2H5)—]n polybutene units and —P— denotesgreater than about 70% [—CH(CH—2CH3)—CH2—]_(n) polyisopropylethyeneunits. The substantially amorphous midblocks —EB_(n)— and —EP_(n)— ofSEB_(n)S and SEP_(n)S (or more simply denoted when n% is greater thanabout 70% as —B— and —P—) are more advantageously when n% is greaterthan about 75%, still more advantageously greater than about 80%, andstill more advantageously greater than about 85%, and even still moreadvantageously greater than about 90% or higher. Typically, highpolybutene content SEB_(n)S or simply SBS is made by adding structuremodifiers, such as ethers, which gives more 1,2 polybutadiene and afterhydrogenation, more polybutene, resulting in less crystallinity, softerblock copolymer, lower viscosity, and higher Tg. Likewise, highpolyisopropylethyene content SEP_(n)S or simply S—P—S is made by addingstructure modifiers to give more 3,4 structure and after hydrogenation,more polyisopropylethyene, resulting in softer block copolymer, lowerviscosity, and higher Tg.

The major advantages of SEB_(n)S and SEP_(n)S over SEBS, SEPS (whenn%=greater than about 70%) is the Tg ofpoly(styrene-ethylene-butylene_(>70)-styrene) andpoly(styrene-ethylene/propyleneisopropylethyene_(>70)-styrene) are muchhigher; the gel rigidities are lower; and the viscosities are muchlower. More specifically, the Tg of SEBS is typically about −58° C. andthe Tg of SEPS is typically about −50 to about −60° C. Whereas, the Tgof SEB_(n)S and SEP_(n)S with high butylene content and highisopropylenethyene content can be advantageously much higher of aboutless than about −40° C., advantageously −30° C. and more advantageouslyhigher of about −27° C. and higher.

It is extraordinary that where typical SEBS and SEPS fluffy amorphousgels fails to provide greater tensile strength, fails to provide greatertear strength, and fails to provide greater resistance to high stressrupture, hereto unknown and unappreciated modification of the midblockstructures provide heretofore unrealizable improved higher tensilestrength, improved higher tear strength, and improved higher resistanceto high stress rupture.

Theory notwithstanding, SEBS and SEPS or fluffy amorphous gels fail toprovide greater improved properties. The following is known:

i) fluffy amorphous gels made from typical SEBS which is created from amixture of 1, 4- and 1,2-polybutadiene to provide a random mixture ofethylene and butylene units greater to suppress crystallinity (as notedby Legge). Such fluffy amorphous gels can not provide greater tearstrength and lack greater resistance to high stress rupture.

ii) fluffy amorphous gels made from typical SEPS which is created byhydrogenation of cis-1,4-polyisoprene results in a 1:1ethylene/propylene elastomer midblock (as noted by Legge). Such fluffyamorphous gels can not provide greater tear strength and lack greaterresistance to high stress rupture.

Contrary to the inferior properties of the above fluffy amorphousgels 1) and 2), the following fluffy crystal gels are found to besuperior and of improve high tear strength, improved resistance to highstress rupture and sufficient greater tensile strength:

iii) fluffy crystal gels made from an admixture of a high crystallineethylene content S—E_(n)B—S block copolymer and a high butylene contentS—EB_(n)—S block copolymer.

iv) fluffy crystal gels made from an admixture of a high crystallineethylene content S—E_(n)B—S block copolymer and a highpolyisopropylenethyene content S—EP_(n)—S block copolymer.

v) fluffy crystal gels made from an admixture of a high crystallineethylene content S—E_(n)B—S block copolymer, a high butylene contentS—EB_(n)—S block copolymer, and a high polyisopropylethyene contentS—EP_(n)—S block copolymer

vi) S—E—EB_(>70)—E—S fluffy crystal gels made by coupling S—E—EB_(>70).

vii) S—E—EP_(>70)—E—S fluffy crystal gels made by coupling S—E—EP_(>70).

viii) fluffy crystal gels made from linear, branched, radial,star-shaped, multi-arm or branched block copolymers having sufficientmultiple midblock components of high crystalline ethylene content, highbutylene content, and/or high isopropylethyene content including allcombinations, sequential additions and permutations and mixtures of suchblock copolymers and as described herein are of the greatest advantage.

Generally, one or more (E) midblocks can be incorporated at variouspositions along the midblocks of the block copolymers. Using thesequential process for block copolymer synthesis. The (E) midblocks canbe positioned as follows:

i) A—E—W—A

ii) A—E—W—E—A

ii) A—W—E—W—A

iii) A—E—W—E—W—E—W—E—A

iv) A—W—E—W—A—E—A—E—W—E—A

v) A—W—A

vi) A—E—A, etc.

The lower flexibility of the block copolymer fluffy crystal gels due tohigh (E) content midblocks can be balanced by the addition ofsequentially formed (W) midblocks. For example, the sequentiallysynthesized block copolymer S—E—EB—S can maintain a high degree offlexibility due to the presence of amorphous —EB— block. The sequentialblock copolymer S—E—EB—B—S can maintain a high degree of flexibility dueto the presence of amorphous —EB— and —B— midblocks. The sequentialblock copolymer S—E—EP—E—S can maintain a high degree of flexibility dueto the presence of —EP— midblock. The sequential block copolymer S—E—B—Scan maintain a high degree of flexibility due to the presence of the —B—midblock. For S—E—S, where the midblock is substantially crystalline andflexibility low, physical blending with amorphous block copolymers suchas S—EB—S, S—B—S, S—EP—S, S—EB—EP—S, (S—EP)_(n) and the like can producemore softer, less rigid, and more flexible fluffy crystal gel.

In additional to the block copolymers S—E—EB—S and S—E—EP—S, such otherblock copolymers such as, for example, S—E—EB—E—S can be made bycoupling S—E—EB and S—E—EP—E—S can be made by coupling S—E—EP or bymaking it sequentially. Multi-arm of such block copolymers can also bemade.

Because of the (E) midblocks, the fluffy crystal gels of the inventionexhibit different physical characteristics and improvements oversubstantially amorphous gels including damage tolerance, improved crackpropagation resistance, improved tear resistance producing knotty tearsas opposed to smooth tears, crystalline melting point of at least 28°C., improved resistance to fatigue, higher hysteresis, etc. Moreover,the fluffy crystal gels when stretched exhibit additional yielding asshown by necking caused by stress induced crystallinity. Additionally,the crystallization rates of the crystalline midblocks can be controlledand slowed depending on thermal history producing time delay recoveryupon deformation. Gels exhibiting time delay recovery followingdeformation is of great advantage and an improvement over fluffyamorphous gels and fluffy crystal gels for certain uses.

Gels having such time delay recovery properties are unique. Such gels ofthe invention can achieve delay times of from about less than 2 secondsto about 20 seconds or more. Characteristic delay times that can beachieved are from about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 40, 50, 60,70, 80, 90, 100, 120, seconds and longer. Consequentially, the recoverycharacteristics of the time delay fluffy gels are due to the stressinduced crystallization of the block copolymers used.

Surprisingly, linear, multiarm, radial, or branched block copolymerswhen formed into gels which exhibit such time delay behavior always havecrystalline —E— component in their midblocks and are characterized ashaving a Brookfield Viscosity value at 5 weight percent solids solutionin toluene at 30° C. of from a bout 120 cps to about 350 cps and higher,advantageously from about 130 cps to about 260 cps and higher, moreadvantageously from about 180 cps to about 380 cps and higher, and stillmore advantageously from about 200 cps to about 800 cps and higher.Additionally, the onset of this strange behavior is observed after themolten gel is allowed to remained undisturbed or unstirred for aselected amount of time before forming into shaped articles. It appearsthat crystallinity, extreme viscosities, cooling, heating and/or shearhistories of the molten gels affects the onset of the time delaybehavior of the room temperature gels.

Regarding the great advantage of the fluffy crystal gels' resistance tofatigue, fatigue (as used herein) is the decay of mechanical propertiesafter repeated application of stress and strain. Fatigue tests giveinformation about the ability of a material to resist the development ofcracks or crazes resulting from a large number of deformation cycles.Fatigue test can be conducted by subjecting samples of fluffy amorphousand crystal gels to deformation cycles to failure (appearance of cracks,crazes, rips or tears in the gels).

Tensile strength can be determined by extending a selected gel sample tobreak as measured at 180° U bend around a 5.0 mm mandrel attached to aspring scale. Likewise, tear strength of a notched sample can bedetermined by propagating a tear as measured at 180° U bend around a 5.0mm diameter mandrel attached to a spring scale.

Various block copolymers can be obtained which are amorphous, highlyrubbery, and exhibiting minimum dynamic hysteresis:

Block copolymer S—EB—S

The monomer butadiene can be polymerized in a ether/hydrocarbon solventto give a 50/50 ratio of 1,2 poly(butadiene)/1,4 poly(butadiene) and onhydrogenation no long runs of —CH₂— groups and negligible crystallinity,i.e., about (0.5)⁴ or 0.06 or 6% and actual crystallinity of about 3%.Due to the constraints of Tg and minimum hysteresis, conventional S—EB—Shave ethylene-butylene ratios of about 60:40 with a crystallinity ofabout (0.6)⁴ or 0.129 or 12% and actual crystallinity of about 7.7%.

Block copolymer S—EP—S

The monomer isoprene when polymerized will produce 95% 1,4poly(isoprene)/5% 3,4 poly(isoprene) and upon hydrogenation will formamorphous, rubbery poly(ethylene-propylene) midblock and no long runs of—CH₂— and no crystallinity.

Mixed block copolymer S—EB/EP—S

The polymerization of a 50/50 mixture of isoprene/butadiene monomers issuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) on hydrogenation will produce a maximum crystallinity of(0.25)⁴ and 0.4%. The actual crystallinity would be approximately about0.2%, which is negligible and results in a good rubbery midblock.

The polymerization of a 80/20 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.10)⁴ or 0.01%. The actual crystallinity would be approximately about0.006%, which is negligible and results in a good rubbery midblock.

The polymerization of a 20/80 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give equal amounts of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.4)⁴ or 2.56%. The actual crystallinity would be approximately about1.53%, which is negligible and results in a good rubbery midblock.

The polymerization of a 20/80 mixture of isoprene/butadiene monomers insuitable ether/hydrocarbon solvents to give a 40:60 ratio of 1,2 and 1,4poly(butadiene) will upon hydrogenation produce a low crystallinity of(0.48)⁴ or 5.3%. The actual crystallinity would be approximately about3.2%, which is negligible and results in a good rubbery midblock.

The percentage that can crystallize is [(—CH₂—)₄]⁴ since this is thechance of getting four (—CH₂—)₄ units in sequence. The percentage thatwill crystallize is about 60% of this. This applies to polymerization ina hydrocarbon solvent. In an ether (eg, diethylether), the percentage(—CH₂—)⁴ units will be reduced so that crystallinity will be negligible.In a mixed ether/hydrocarbon solvent, values will be intermediate,depending on the ratio of ether to hydrocarbon.

The midblocks (Z) of one or more —E—, —B—, —EB—, or —EP— can comprisevarious combinations of midblocks between the selected end blocks (A);these include: —E—EB—, —E—EP—, —B—EP—, —B—EB—, —E—EP—E—, —E—EB—B—,—B—EP—B—, —B—EB—B—, —E—B—EB—, —E—B—EP—, —EB—EP—, —E—EB—EP—, —E—EP—EB—,—B—EB—EP—, —B—EP—EB—, —E—EP—E—EP—, —E—EP—E—EB—, —B—EP—B—EP—,—B—EB—B—EB—, —B—EB—B—EP—, —E—EB—B—EP—, —E—EP—B—EB—, E—EP—E—EP—E—,—B—EP—B—EP—B—, —E—EP—E—EB—, —E—EP—E—EP—EB—, —E—EP—E—EP—E—,—E—EP—EB—EP—EB—B— and the like.

The block copolymers of (A—Z—A) can be obtained by sequential synthesismethods followed by hydrogenation of the midblocks. As denoted above,abbreviations are interchangeably used, for example (S—E—EP—S) denotespoly(styrene-ethylene-ethylene-co-propylene-styrene). Other linear blockcopolymers (denoted in abbreviations) include the following: (S—E—S),(S—Butylene—S), (S—E—EB—S), (S—E—EP—S), (S—B—EP—S), (S—B—EB—S),(S—E—EP—E—S), (S—E—EB—B—S), (S—B—EP—B—S), (S—B—EB—B—S), (S—E—B—EB—S),(S—E—B—EP—S), (S—EB—EP—S), (S—E—EB—EP—S), (S—E—EP—EB—S), (S—B—EB—EP—S),(S—B—EP—EB—S), (S—E—EP—E—EP—S), (S—E—EP—E—EB—S), (S—EP—B—EP—S),(S—B—EB—B—EB—S), (S—B—EB—B—EP—S), (S—E—EB—B—EP—S), (S—E—EP—B—EB—S),(S—E—EP—E—EP—E—S), (S—B—EP—B—EP—B—S), (S—EP—E—EB—S), (S—E—EP—E—EP—EB—S),(S—E—EP—E—EP—E—S), (S—E—EP—EB—EP—EB—B—S), (S—E—EP—EB—EP—EB . . . —S) andthe like.

The multi block star-shaped (or radial) copolymers (Z—Z)_(n)X can beobtained by sequential synthesis methods including hydrogenation ofselected block copolymers made by polymerizing half of the blockcopolymers such as SBS or SIS and couple the halves with a couplingagent such as an organic dihalide; or couple with an agent such asSnCl4, which results in star-shaped block copolymers (four branches).Coupling with divinyl benzene give block copolymers which are veryhighly branched. Radial block copolymers suitable for use in forming thefluffy crystal gels of the present invention include: (S—E)_(n),(S—E—EB)_(n), (S—E—EP)_(n), (S—B—EP)_(n), (S—B—EB)_(n), (S—E—EP—E)_(n),(S—E—EB—B)_(n), (S—B—EP—B)_(n), (S—B—EB—B)_(n), (S—E—B—EB)_(n),(S—E—B—EP)_(n), (S—EB—EP)_(n), (S—E—EB—EP)_(n), (S—E—EP—EB)_(n),(S—B—EB—EP)_(n), (S—B—EP—EB)_(n), (S—E—EP—E—EP)_(n), (S—E—EP—E—EB)_(n),(S—EP—B—EP)_(n), (S—B—EB—B—EB)_(n), (S—B—EB—B—EP)_(n),(S—E—EB—B—EP)_(n), (S—E—EP—B—EB)_(n), (S—E—EP—E—EP—E)_(n),(S—B—EP—B—EP—B)_(n), (S—E—EP—E—EB)_(n), (S—E—EP—E—EP—EB)_(n),(S—E—EP—E—EP—E)_(n), (S—E—EP—EB—EP—EB—B)_(n) and counter partmultifunctional block copolymers: (R)_(n)—R—S, (R)_(n)—E—EB—S,(R)_(n)—E—EP—S, (R)_(n)—E—EP—E—S, (R)_(n)—E—EB—B—S, (R)_(n)—E—B—EB—S,(R)_(n)—E—B—EP—S, (R)_(n)—E—EB—EP—S, (R)_(n)—E—EP—EB—S,(R)_(n)—E—EP—E—EP—S, (R)_(n)—E—EP—E—EB—S, (R)_(n)—E—EB—B—EP—S,(R)_(n)—E—EP—B—EB—S, (R)_(n)—E—EP—E—EP—E—S, (R)_(n)—E—EP—E—EB—S,(R)_(n)—E—EP—E—EP—EB—S, (R)_(n)—E—EP—E—EP—E—S,(R)_(n)—E—EP—EB—EP—EB—B—S, (R)_(n)—E—EP—EB—EP—EB . . . —S, and the like.In the above notation, “—E—” denotes substantially crystallinepolyethylene midblock.

The selected amount of crystallinity in the midblock should besufficient to achieve improvements in one or more physical propertiesincluding improved damage tolerance, improved crack propagationresistance, improved tear resistance, improved resistance to fatigue ofthe bulk gel and resistance to catastrophic fatigue failure of fluffycrystal gel composites, such as between the surfaces of the fluffycrystal gel and substrate or at the interfaces of the interlockingmaterial(s) and fluffy crystal gel, which improvements are not found inamorphous gels at corresponding gel rigidities.

Selected linear block and radial copolymers utilized in forming thefluffy crystal gels of the invention are characterized as having anethylene to butylene midblock ration (E:B), an ethylene toethylene/propylene (E:EP) ratio, and an ethylene to ethylene/butylene(E:EB) ratio of about 85:15 to about 65:35. Advantageously, the butyleneconcentration of the midblock is about 35% or less, more advantageously,about 30% or less, still more advantageously, about 25% or less,especially advantageously, about 20% or less. Advantageously, theethylene to butylene midblock ratios can range from about 89:11, 88:12,87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22,77:23, 76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32,67:33, 66:34 to about 65:35.

The A to Z midblock ratio of the block copolymers suitable for formingfluffy crystal gels of the invention can range from about 20:80 to 40:60and higher. More specifically, the value can be 15:85, 19:81, 20:80,21:79, 22:78, 23:77, 24:76, 25:75, 26:74, 27:73, 28:72, 29:71, 30:70,31:69, 32:68, 33:67, 34:66, 35:65, 36:64, 37:63, 38:62, 39:61, 40:60,41:59, 42:58, 43:57, 44:65, 45:55, 46:54, 47:53, 48:52, 49:51, 50:50,51:49 and 52:48.

As described above, the G_(n) can also be made with or without a (IV)selected minor amount (from about less than 0.5% to about 10% or more)of at least one polar polymer components such as copolymer selected fromthe group consisting of ethylene-butyl acrylate, ethylene-ethylacrylate, ethylene-methyl acrylate, ethylene-vinyl acetate,ethylene-vinyl acrylate, ethylene-vinyl alcohol,acrylonitrile-styrene-acrylate, styrene-acrylonitrile, styrene-maleicanhydride, meleated poly(styrene-ethylene-propylene-styrene) or meleatedpoly(styrene-ethylene-butylene-styrene) and the like. Such polarcomponents are more compatible with the polar thermoplastic microspheresas well as co-compatibility with the non-polar components of the blockcopolymers forming the fluffy gels of the invention. Such polaradditives can counteract to some degree the lowering of the physicalproperties due to increasing amounts of microsphere needed to achievelower densities of the fluffy gels.

The insulating gels and extraordinary fluffy gels can comprise selectedmajor or minor amounts of one or more additional crystalline ornon-crystalline polymers or copolymers (V) described above, provided theamounts and combinations are selected do not substantially decreasingthe desired properties. Such V components also include polyethyleneoxide(EO), poly(dimethylphenylene oxide), teflon, optical clear amorphouscoopolymers based on 2,2-bistrifluoromethyl-4,5-difluoro-1,3-dioxol(PDD) and tetrafluoroethylene (TFE) and the like. Still other (V)polymers include homopolymers which can be utilized in minor amounts;these include: polystyrene, polydimethylsiloxane, polyolefins such aspolybutylene, polyethylene, polyethylene copolymers, polypropylene (suchas Dow polypropylene homopolymers H700-12, 700-12A, 700-12NA, 701-20,702-35, 704, 705, 103-00, 303-02, 500-35, 501, 104, 505; polypropylenecopolymers C101-00, C102-04, C103-04, C707-12, C707-12, C707-12U,C702-20, C708-21U, C709-30, C700-35N, C703-35U, and the like.Polyurethane elastomers based on saturated hydrocarbon dios (Handlin,D., Chin. S., and Masse, M., et al. “POLYURETHANE ELASTOMERS BASED ONNEW SATURATED HYDROCARBON DIOLS” Published Society of Plastics Industry,Polyurethane Division, Las Vegas, Oct. 23, 1996) are also suitable foruse in blending with the block copolymers (I) used in forming the gelsor fluffy crystal gels of the invention. Such saturated hydrocarbondiols include hydroxyl terminated oligomers of poly(ethylene—butylene)(EB), poly(ethylene—propylene) (EP), —E—EB—, —E—EP—, —B—EP—, —B—EB—,—E—EP—E—, —E—EB—B—, —B—EP—B—, —B—EB—B—, —E—B—EB—, —E—B—EP—, —EB—EP—,—E—EB—EP—, —E—EP—EB—, —B—EB—EP—, —B—EP—EB—, —E—EP—E—EP—, —E—EP—E—EB—,—B—EP—B—EP—, —B—EB—B—EB—, —B—EB—B—EP—, —E—EB—B—EP—, —E—EP—B—EB—,—E—EP—E—EP—E—, —B—EP—B—EP—B—, —E—EP—E—EB—, —E—EP—E—EP—EB—,—E—EP—E—EP—E—, —E—EP—EB—EP—EB—B— and the like. As an example,thermoplastic polyurethane (TPU) made with diisocyanates and chainextenders such as 2,2,4-trimethyl-1,3-pentanediol (TMPD) and2-Butyl-2-ethyl-1,3-pentanediol (BEPD) from saturated hydrocarbon diolKLP L-2203 having a hard segment contents of 22% exhibits clean phaseseparation of the hard and soft segments with a glass transition of −50°C. TPU polyurethane elastomers based on KLP L-2203 diol, MDI with TMPMand BEPD chain extenders at 22% hard segment, 104 isocyanate index, andcured at 105° C. gives 2,430 and 1,160 tensile psi, 1040% and 2180%elongation at break, and modulus at 300% elongation of 670 and 290 psirespectively by the one shot method. Polyurethane elastomers prepared bythe one shot method based on KLP L-2203, MDI and TMP at 1.04 NCO/OHratio having hard segment concentrations of 22%, 33% and 44% givetensile of 2430, 2830 and 2760 psi respectively, elongations at break of1040%, 830%, and 760% respectively, and modulus at 300% elongation of670, 1160 and 1360 psi respectively. KLP L-2203 (hydroxyl terminatedpoly(ethylene-butylene) oligomer (50,000 cps at 20° C.) based TPU's canbe mixed with the crystalline block copolymers to form soft fluffycrystal gels within the gel rigidity ranges of the invention. Thethermoplastic crystalline triblock and multiblock polyurethaneelastomers can also be blended by themselves with components II and IIIto make strong, elastic fluffy gels of the invention. Hence,thermoplastic polyurethanes with hard segment contents of from aboutless than 22% to about 45% and higher are of great advantage in formingthe fluffy gels of the invention.

Suitable V components for use in the present invention includepolyolefins (polyethylene and polyethylene copolymers), such as DowChemical Company's Dowlex 3010, 2021D, 2038, 2042A, 2049, 2049A, 2071,2077, 2244A, 2267A; Dow Afinity ethylene alpha-olefin resin PL-1840,SE-1400, SM-1300; more suitably: Dow Elite 5100, 5110, 5200, 5400,Primacor 141—XT, 1430, 1420, 1320, 3330, 3150, 2912, 3340, 3460; DowAttane (ultra low density ethylene-octene-1 copolymers) 4803, 4801, 4602and the like. Polyolefins such as these (in minor amounts) can improvethe tear and rupture resistance of the compositions of the invention dueto their crystalline contributions.

The conventional term “major” means about 51 weight percent and higher(e.g. 51%, 52%, 55%, 60%, 65%, 70%, 75%, 80% and the like) and the term“minor” means 49 weight percent and lower (e.g. 1%, 2%, 5%, 10%, 15%,20%, 25% and the like).

Additional example of polymers, copolymers, and blends include: (a)Kraton G 1651, G 1654X; (b) Kraton G 4600; (c) Kraton G 4609; othersuitable high viscosity polymer and oils include: (d) Tuftec H 1051; (e)Tuftec H 1041; (f) Tuftec H 1052; (g) Kuraray S—E—EP—S 4033; (h) KurarayS—EB—S 8006; (i) Kuraray SEPS 2005; (j) Kuraray SEPS 2006, and (k)blends (polyblends) of (a)-(h) with other polymers and copolymersinclude: (1) S—EB—S/SBS; (2) S—EB—S/SIS; (3) S—EB—S/(SEP); (4)S—EB—S/(SEB)_(n); (5) S—EB—S/(SEB)_(n); (6) S—EB—S/(SEP)_(n); (7)S—EB—S/(SI)_(n); (8) S—EB—S/(SI) multiarm; (9) S—EB—S/(SEB)_(n); (10)(SEB)_(n) star-shaped copolymer; (911) s made from blends of (a)-(k)with other homopolymers include: (12) S—EB—S/polystyrene; (13)S—EB—S/polybutylene; (14) S—EB—S/poly-ethylene; (14)S—EB—S/polypropylene; (16) SEP/S—EB—S, (17) SEP/SEPS, (18) SEP/SEPS/SEB,(19), SEPS/S—EB—S/SEP, (20), SEB/S—EB—S (21), EB—EP/S—EB—S (22),S—EB—S/EB (23), S—EB—S/EP (24), (25) (SEB)_(n) s, (26) (SEP)_(n), (27)Kuraray 2007 (SEPS), (28) Kuraray 2002, (SEPS), (29) Kuraray 4055(S—E—EP—S (30) Kuraray 4077 (S—E—EP—S) (31) Kuraray 4045 (S—E—EP—S) (32)(S—EB—EP)_(n), (33) (SEB)_(n), (34) EPDM, (35) EPR, (36) EVA, (37) coPP,(38) EMA, (39) EEA, (40) DuPont Teflon AF amorphous fluoropolymers, (41)Dow polydimethylsiloxane, (42) maleated S—EB—S (maleation level 2-30%),(43) (EP)_(n), GRP-6918 (SEPS), G1730 (SEPSEP), G1780 (SEP)n, GRP-6906(SEPS), GRP-6917 (SEBS), KX-219, KX-222, KX-605, RP-6919 (SEBIS) and thelike.

Representative examples of commercial elastomers that can be combinedwith the block copolymers (I) described above include: Shell KratonsD1101, D1102, D1107, D1111, D1112, D1113X, D1114X, D1116, D1117, D1118X,D1122X, D1125X, D1133X, D1135X, D1184, D1188X, D1300X, D1320X, D4122,D4141, D4158, D4240, D1144, D1184, G1650, G1652, G1654, RP6917, G1657,G1701X, G1702X, G1726X, G1750X, G1765X, FG1901X, FG1921X, D2103, D2109,D2122X, D3202, D3204, D3226, D5298, D5999X, D7340, G1650, G1651, G1652,G4609, G4600, G1654X, G2701, G2703, G2705, G1706, G2721X, G7155, G7430,G7450, G7523X, G7528X, G7680, G7705, G7702X, G7720, G7722X, G7820,G7812X, G7827, G7890X, G7940, G1730M, FG1901X and FG1921X. Kuraray'sSEP, SEPS, S—EB—S, S—EB—EP—S Nos. 1001, 1050, 2027, 2003, 2006, 2007,2008, 2023, 2043, 2063, 2050, 2103, 2104, 2105, 4033 (S—E—EP—S), 4045(S—E—EP—S), 4055 (S—E—EP—S), 4077 (S—E—EP—S), 8004, 8006, 8007, H-VS-3(S-V-EP)n, Kraton G 1901, 1921, 1924 and the like.

The block copolymers can have a broad range of styrene toethylene-butylene ratios (S:EB) and styrene to ethylene-propylene ratios(S:EP) of about 20:80 or less to about 40:60 or higher. The S:EB weightratios can range from lower than about 20:80 to above about 40:60 andhigher.

The Brookfield Viscosity of a 5 weight percent solids solution intoluene at 30° C. of 2006, 4045, 4055, 4077 typically range about 20-35,about 25-150, about 60-150, about 200-400 respectively. TypicalBrookfield Viscosities of a 10 weight percent solids solution in tolueneat 30° C. of 1001, 1050, 2007, 2063, 2043, 4033, 2005, 2006, are about70, 70, 17, 29, 32, 50, 1200, and 1220 respectively. Typical BrookfieldViscosity of a 25 weight percent solids solution in toluene at 25° C. ofKraton D1101, D1116, D1184, D1300X, G1701X, G1702X are about 4000, 9000,20000, 6000, 50000 and 50000 cps respectively. Typical BrookfieldViscosity of a 10 weight percent solids solution in toluene at 25° C. ofG1654X is about 370 cps. The Brookfield Viscosities of a 20 and 30weight percent solids solution in toluene at 30° C. of H-VS-3 are about133 cps and 350 cps respectively.

Suitable block copolymers and their typical viscosities are furtherdescribed. Shell Technical Bulletin SC:1393-92 gives solution viscosityas measured with a Brookfield model RVT viscometer at 25° C. for KratonG 1654X at 10% weight in toluene of approximately 400 cps and at 15%weight in toluene of approximately 5,600 cps. Shell publication SC:68-79gives solution viscosity at 25° C. for Kraton G 1651 at 20 weightpercent in toluene of approximately 2,000 cps. When measured at 5 weightpercent solution in toluene at 30° C., the solution viscosity of KratonG 1651 is about 40. Examples of high viscosity S—EB—S triblockcopolymers include Kuraray's S—EB—S 8006 which exhibits a solutionviscosity at 5 weight percent at 30° C. of about 51 cps. Kuraray's 2006SEPS polymer exhibits a viscosity at 20 weight percent solution intoluene at 30° C. of about 78,000 cps, at 5 weight percent of about 27cps, at 10 weight percent of about 1220 cps, and at 20 weight percent78,000 cps. Kuraray SEPS 2005 polymer exhibits a viscosity at 5 weightpercent solution in toluene at 30° C. of about 28 cps, at 10 weightpercent of about 1200 cps, and at 20 weight percent 76,000 cps. Othergrades of S—EB—S, SEPS, (SEB)_(n), (SEP)_(n) polymers can also beutilized in the present invention provided such polymers exhibits therequired high viscosity. Such S—EB—S polymers include (high viscosity)Kraton G 1855X which has a Specific Gravity of 0.92, BrookfieldViscosity of a 25 weight percent solids solution in toluene at 25° C. ofabout 40,000 cps or about 8,000 to about 20,000 cps at a 20 weightpercent solids solution in toluene at 25° C.

The styrene to ethylene and butylene (S:EB) weight ratios for the Shelldesignated polymers can have a low range of 20:80 or less. Although thetypical ratio values for Kraton G 1651, 4600, and 4609 are approximatelyabout 33:67 and for Kraton G 1855X approximately bout 27:73, Kraton G1654X (a lower molecular weight version of Kraton G 1651 with somewhatlower physical properties such as lower solution and melt viscosity) isapproximately about 31:69, these ratios can vary broadly from thetypical product specification values. In the case of Kuraray's S—EB—Spolymer 8006 the S:EB weight ratio is about 35:65. In the case ofKuraray's 2005 (SEPS), and 2006 (SEPS), the S:EP weight ratios are 20:80and 35:65 respectively. The styrene to ethylene-ethylene/propylene(S:E—EP) ratios of Kuraray's SEPTON 4044, 4045, 4055, and 4077(S—E—EP—S) are typically about 37.6, 30, 30 respectively. More typicallythe (S:E—EP) and (S:EP) ratios can vary broadly much like S:EB ratios ofS—EB—S and (SEB)_(n) from less than 19:81 to higher than 51:49 (asrecited above) are possible. It should be noted that multiblockcopolymers including SEPTON 4033, 4045, 4055, 4077 (S—E—EP—S) and thelike are described in my cited copending parent applications and are thesubject matter of related inventions.

The block copolymers such as Kraton G 1645X having ratios of 31:69 orhigher can be used and do exhibit about the same physical properties inmany respects to Kraton G 1651 while Kraton G 1654X with ratios below31:69 may also be use, but they are less advantageous due to theirdecrease in the desirable properties of the final gel.

Plasticizers (II) particularly advantageous for use in practicing thepresent invention are will known in the art, they include rubberprocessing oils such as paraffinic and naphthenic petroleum oils, highlyrefined aromatic-free paraffinic and naphthenic food and technical gradewhite petroleum mineral oils, and synthetic liquid oligomers ofpolybutene, polypropene, polyterpene, etc. The synthetic series processoils are high viscosity oligomers which are permanently fluid liquidnonolefins, isoparaffins or paraffins of moderate to high molecularweight.

The amount of plasticizing oil (II) sufficient to achieve gel rigiditiesof from less than about 2 gram Bloom to about 3,000 gram Bloom rangefrom less than about 250 to about 2,000 parts by weight of aplasticizing oil.

Examples of representative commercially available plasticizing oilsinclude Amoco® polybutenes, hydrogenated polybutenes, polybutenes withepoxide functionality at one end of the polybutene polymer, liquidpoly(ethylene/butylene), liquid hetero-telechelic polymers ofpoly(ethylene-butylene-styrene) with epoxidized polyisoprene andpoly(ethylene/butylene) with epoxidized polyisoprene: Example of suchpolybutenes include: L-14 (320 M_(n)), L-50 (420 M_(n)), L-100 (460M_(n)), H-15 (560 M_(n)), H-25 (610 M_(n)), H-35 (660 M_(n)), H-50 (750M_(n)), H-100 (920 M_(n)), H-300 (1290 M_(n)), L-14E (27-37 cst @ 100°F. Viscosity), H-300E (635-690 cst @ 210° F. Viscosity), Actipol E6 (365M_(n)) E16 (973 M_(n)), E23 (1433 M_(n)), Kraton KLP L-2203 and KratonKLP L-1203, EKP-206, EKP-207, HPVM-2203 and the like. Example of variouscommercially oils include: ARCO Prime (55, 70, 90, 200, 350, 400 and thelike), Duraprime and Tufflo oils (6006, 6016, 6016M, 6026, 6036, 6056,6206, etc), other white mineral oils include: Bayol, Bernol, American,Blandol, Brakeol, Ervol, Gloria, Kaydol, Litetek, Lyondell (Duraprime55, 70, 90, 200, 350, 400, etc), Marcol, Parol, Peneteck, Primol,Protol, Sontex, Witco brand white oils including RR-654-P and the like.Generally, plasticizing oils with average molecular weights less thanabout 200 and greater than about 700 may also be used (e.g., H-300 (1290M_(n))).

Comparisons of oil extended S—EB—S triblock copolymers have beendescribed in Shell Chemical Company Technical Bulletin SC:1102-89 (April1989) “KRATON® THERMOPLASTIC RUBBERS IN OIL GELS” which is incorporatedherein by reference.

Of great advantage are the unexpanded particulate materials which can bedispersed and within a controlled temperature heating range can producea predetermined volume of closed cell particulate dispersions formingthe fluffy gels. The particulate materials useful are unexpandedmicrospheres of poly(acrylonitrile-methacrylonitrile) copolymersencapsulated liquid isopentane which are available from Akzo Nobel bythe tradename Expancel. The thermoplastic microspheres comprises atleast about 80% weight of copolymer and about 6 to about 16% isopentaneand are further characterized as having a unexpanded relative density ofabout 1.2 (H₂O=1.0), particle size of about 3 to about 50 microns, aT_(start) or softing temperature of about 106° C. to about 135° C. and adecomposition of rupturing temperature T_(max) of about 138° C. to about195° C. The unexpanded thermoplastic microspheres are activated by heatand expand to approximately about 50 times its unexpanded size toprovide an average particle density of about less than about 0.020specific gravity. Their lowest calculated density reached at T_(max)during TMA test is between about 0.25 to about 0.017 g/cm³. Morespecifically, unexpanded grades of microspheres include grades followedby (range of temperatures T_(start)° C./T_(max)° C.): #051(106-111/138-147), #053 (95-102/137-145), #054 (125-135/140/150), #091(118-126/161-171), #091-80 (118-126/171-181), and #092-120(118-126/185-195). Other expandable thermoplastic microspheres can be ofadvantage in making the fluffy gels of the invention. Such should be ofhigher temperature activated unexpanded thermoplastic microspheres withliquid isopentane, isobutane cores, and the like. Suitably higherT_(start) and T_(max) temperature unexpanded thermoplastic microspherescontemplated for use in the present invention can have(T_(start)/T_(max)) of about (110° C./200° C.), (100° C./205° C.), (100°C./210° C.), (100° C./215° C.), (100° C./220° C.). (100° C./225° C.),(100° C./235° C.) and higher.

Fluffy gels of the invention of densities of about 0.6 g/cm³ comprisesabout at least above about 5%-6% by weight of unexpanded microspheres,at about 0.5 g/cm³, the amount of microspheres is approximately about10%-11% by weight, at about 0.4 g/cm³, the amount of microspheres isabout 12%-15%, and at about 0.3 g/cm³, the amount of microspheres isabout 18%-20% or higher. Higher density gels (about 0.7 g/cm³ and about0.8 g/cm³) can also be made following the teachings of the presentinvention. Suitable amounts of unexpanded microspheres useful informingthe fluffy gels of the invention can range from about less than 5% to30% or higher, more suitably, from about 5% to 25% or higher, and stillmore suitably, from about 5% to about 20% or higher. As the densities ofthe fluffy gels of the invention is made less and less, the physicalproperties of the fluffy gels also are more and more affected. Thefluffy crystal gel physical properties remain substantially higher thanthe physical properties of the fluffy amorphous gels of the invention.This is due to the crystalline contributions as described earlier.

Microspheres incapable of softing by heat and therefore are unexpandableor remains unexpanded, such as phenolic microspheres are not suitablefor making the fluffy gels of the present invention because phenolic, aheat-cured thermoset, is the reaction product of phenol and formaldehydeand the structured formed gives it heat resistance, dimensionalstability, creep resistance and hardness. Likewise glass microspheres,metal, quartz, and carbon microspheres and the like are not suitable foruse in making gels having high concentration of microspheres. Suchmicrospheres, however, are suitable for making gels having lowconcentration of microspheres.

Accordingly, a selected amount of one or more of the heat activatedunexpanded thermoplastic particulate materials are dispersed in anordered, random, homogeneous, nonhomogeneous, stratified, partiallystratified or one or more separated phases. The dispersed unexpandedparticulate materials are capable of producing a predetermined volume ofclosed cell particulate dispersion forming the fluffy gels withdensities of at least less than about 0.60 g/cm3. The fluffy gelsfurther having a gel rigidity of from about 20 to about 3,000 gramBloom, and an elongation of at least 200%. Typical densities which canbe achieved can range from greater than about 0.6 g/cm3 to less thatabout 0.3 g/cm3. Fluffy gel densities of about 0.75, 0.70, 0.65, 0.60,0.55, 0.50, 0.45, 0.40, 0.35, 0.30 or lower can be achieved using theunexpanded particulate materials.

The fluffy gels can be made non-adhearing, non-sticking, (non-tacky), byincorporating an advantage amount of stearic acid (octadecanoic acid),metal stearates (e.g., calcium stearate, maGnesium stearate, zincstearate, etc.), polyethylene glycol distearate, polypropylene glycolester or fatty acid, and polytetramethylene oxide glycol disterate,waxes, stearic acid and waxes, metal stearate and waxes, metal stearateand stearic acid. The use of stearic acid alone do not reduce tack. Theamount of stearic acid is also important. As an example, ratio of 200grams stearic acid to 2,000 gram of S—EB—S (a ratio of 0.1) will resultin spotted tack reduction on the surface of the gel. A ratio of 250 to2,000 will result in spotted crystallized stearic acid regions on thesurface of the gel or spotted tack reduction. A ratio of 300 to 2,000will result in complete tack reduction with large stearic acidcrystallized regions on the surface of the gel. When microcrystallinewaxes are incorporated together with stearic acid, the crystallizationof stearic acid completely disappears from the surface of the gel. Forexample excellent result is achieved with 200 grams of stearic acid, 150grams of microcrystalline wax and 2,000 grams of S—EB—S. The sameexcellent result is achieved when S—EB—S is adjusted to 3,000 grams,4,000 grams, etc. The same result is achieved with (I) copolymers aswell as in combination with polymers (II) such as SEPS, S—EB—EP—S,(S—EB—EP)_(n), (SEB)_(n) polymers. Moreover, when about 50 grams oftetrakis[methylene 3,-(3′5′-di-tertbutyl-4″-hydroxyphenyl)propionate]methane is use (per about 50 lbs of gel) as a tack reducing bloomingagent, tack is completely removed from the surface of the gel after twoor three weeks of blooming.

The fluffy crystal gels can also contain useful amounts ofconventionally employed additives such as stabilizers, antioxidants,antiblocking agents, colorants, fragrances, flame retardants, flavors,other polymers in minor amounts and the like to an extend not affectingor substantially decreasing the desired properties. Additives in varyingamounts useful in the gels of the present invention include:tetrakis[methylene 3,-(3′5═-di-tertbutyl-4″-hydroxyphenyl) propionate]methane, octadecyl 3-(3″,5″-di-tert-butyl-4″-hydroxyphenyl) propionate,distearyl-pentaerythritol-diproprionate, thiodiethylenebis-(3,5-ter-butyl-4-hydroxy) hydrocinnamate,(1,3,5-trimethyl-2,4,6-tris[3,5-di-tert-butyl-4-hydroxybenzyl] benzene),4,4″-methylenebis(2,6-di-tert-butylphenol), stearic acid, oleic acid,stearamide, behenamide, oleamide, erucamide, N,N″-ethylenebisstearamide,N,N″-ethylenebisoleamide, sterryl erucamide, erucyl erucamide, oleylpalmitamide, stearyl stearamide, erucyl stearamide, calcium sterate,other metal sterates, waxes (e.g., polyethylene, polypropylene,microcrystalline, carnauba, paraffin, montan, candelilla, beeswax,ozokerite, ceresine, and the like), teflon (TFE, PTFE, PEA, FEP, etc),polysiloxane, etc. the fluffy crystal gel can also contain metallicpigments (aluminum and brass flakes), TiO2, mica, fluorescent dyes andpigments, phosphorescent pigments, aluminatrihydrate, antimony oxide,iron oxides (Fe₃O₄, —Fe₂O₃, etc.), iron cobalt oxides, chromium dioxide,iron, barium ferrite, strontium ferrite and other maGnetic particlematerials, molybdenum, silicones, silicone fluids, lake pigments,aluminates, ceramic pigments, ironblues, ultramarines, phthalocynines,azo pigments, carbon blacks, silicon dioxide, silica, clay, feldspar,glass microspheres, barium ferrite, wollastonite and the like. Thereport of the committee on MaGnetic Materials, Publication NMAB-426,National Academy Press (1985) is incorporated herein by reference.

The fluffy gels can be made into composites. The gels can be castedunto, pressured molded, injection molded and various methods of formingwith or interlocking with various substrates, such as open cellmaterials, metals, ceramics, glasses, and plastics, elastomers,fluoropolymers, expanded fluoropolymers, Teflon (TFE, PTFE, PEA, FEP,etc), expanded Teflon, spongy expanded nylon, etc.; the molten crystalgel is deformed as it is being cooled. Useful open-cell plasticsinclude: polyamides, polyimides, polyesters, polyisocyanurates,polyisocyanates, polyurethanes, poly(vinyl alcohol), etc. Suitableopen-celled Plastic (sponges) are described in “Expanded Plastics andRelated Products”, Chemical Technology Review No. 221, Noyes Data Corp.,1983, and “Applied Polymer Science”, Organic Coatings and PlasticChemistry, 1975. These publications are incorporated herein byreference.

Not only are the (G_(n)M_(m)) useful for insulating the body andselectively prevent generation of body moisture, sandwiches of fluffygel-material, fluffy gel-material-fluffy gel or material-fluffygel-material are useful as shock absorbers, acoustical isolators,vibration dampers, vibration isolators, and wrappers. For example thevibration isolators can be use under research microscopes, officeequipment, tables, and the like to remove background vibrations. Thetear resistance nature of the instant fluffy crystal gels are superiorin performance to fluffy amorphous gels which are much less resistanceto crack propagation caused by long term continue dynamic loadings.

The fluffy gel articles can be formed by blending, injection molding,extruding, spinning, casting, dipping and other conventional methods.For example, Shapes having various cross-section can be extruded. Thefluffy crystal gels can also be formed directly into articles orremelted in any suitable hot melt applicator and extruded into shapedarticles and films or spun into threads, strips, bands, yarns, or othershapes.

The fluffy gels are excellent for cast, injection, or spinning moldingand the molded products have high tear resistance characteristics whichcannot be anticipated form the properties of the raw components. Otherconventional methods of forming the composition can be utilized.

It is found that orientation substantially affects the properties of thefluffy gels as well as non-fluffy gels made from the (I) copolymers ofthe invention. A non-fluffy gel is a gel which is void of themicrosphere particulate dispersion of the fluffy gels. In other words aplain optically clear gel. The effect of orientation is noted asfollows: when a optically clear gel is extruded by conventional means,such as under high pressure or experience extreme high tension andextension while being rapidly cooled, the gel may become tough in theradial direction and very weak in the transverse direction. This may bebecause in rapid extension and cooling of the melt or molten gel, thestyrene domains forms cylindrically along the transverse axis in thesolid state and is very weak under tension. It may be possible to curethis weakness by annealing the extruded gel at or near the polystyrenemelting point. On the other hand, When an optically clear gel isextruded by a rotating cone or plate elastic energy method of extrusion,the extruded gel can also become highly oriented, but in the radialdirection which results in a very strong gel when extended in thetransverse direction as well as a tough gel in the radial direction.Consequently, oriented fluffy gels can be very weak or strong dependingon the methods selected for making articles from such fluffy gels.

Not only do the fluffy gels have all the desirable combination ofphysical and mechanical properties substantially similar to highviscosity amorphous S—EB—S gels such as high elongation at break of atleast 1,600%, ultimate tensile strength of about 8×10⁵ dyne/cm² andhigher, low elongation set at break of substantially not greater thanabout 2%, substantially about 100% snap back when extended to 1,200%elongation, and a gel rigidity of substantially from about 2 gram toabout 3,000 gram Bloom and higher, the fluffy gels of the presentinvention exhibit improved tear resistance and resistance to fatigue notobtainable from amorphous S—EB—S or S—EP—S gels at corresponding gelrigidities.

The fluffy gels of the present invention exhibit one or more of thefollowing properties. These are: (1) tensile strength of about from lessthan about 8×10⁵ dyne/cm² to about 10⁷ dyne/cm² and greater; (2)elongation of less than about 200% to about 3,000% and higher; (3)elasticity modules of less than about 10⁴ dyne/cm² to about 10⁶ dyne/cm²and greater; (4) shear modules of less than about 10⁴ dyne/cm² to about10⁶ dyne/cm² and greater as measured with a 1, 2, and 3 kilogram load at23° C.; (5) gel rigidity of about less than about 2 grams Bloom to about3,000 gram Bloom and higher as measured by the gram weight required todepress a gel a distance of 4 mm with a piston having a cross-sectionalarea of 1 square cm at 23° C.; (6) tear propagation resistance from lessthan about 1.5 kg/cm to about 5.6 kg/cm or higher (the tear resistanceof fluffy crystal gels being advantageously greater than that of fluffyamorphous gels); (7) resistance of the fluffy crystal gels to fatiguebeing advantageously greater than the fatigue resistance of fluffyamorphous gels at corresponding gel rigidities; (8) and substantially100% snap back recovery when extended at a crosshead separation speed of25 cm/minute to 200% at 23° C. Properties (1), (2), (3), and (6) aboveare measured at a crosshead separation speed of 25 cm/minute at 23° C.

The molded fluffy crystal (—E— midblock segment) gel articles haveadditional important advantages in that the end-use performanceproperties are advantageously greater than amorphous —EB— and —EP—midblock segment block copolymer gels in that they are more resistant tocracking, tearing, crazing or rupture in flexural, tension, compression,or other deforming conditions of use. Like amorphous gels, the moldedarticles made from the instant composition possess the intrinsicproperties of elastic memory enabling the articles to recover and retainits original molded shape after many extreme deformation cycles.

Not only is the fluffy gels of the invention advantageous for use inmaking toys, the novel fluffy crystal gels because of their improvedproperties find other practical uses. Because of their improved tearresistance and improved resistance to fatigue, the fluffy crystal gelsof the present invention achieve greater performance than amorphous gelsin low frequency vibration applications, such as viscoelastic layers inconstrained-layer damping of mechanical structures and goods, asviscoelastic layers used in laminates for isolation of acoustical andmechanical noise, as anti-vibration elastic support for transportingshock sensitive loads, as vibration isolators for an optical table, asviscoelastic layers used in wrappings, enclosures and linings to controlsound, as compositions for use in shock and dielectric encapsulation ofoptical, electrical, and electronic components.

Because of their improved tear resistance and improved resistance tofatigue, the fluffy crystal gels are more useful as molded shapearticles for use in medical and sport health care, such use includetherapeutic hand exercising grips, dental floss, crutch cushions,cervical pillows, bed wedge pillows, leg rest, neck cushion, mattress,bed pads, elbow padding, dermal pads, wheelchair cushions, helmet liner,cold and hot packs, exercise weight belts, traction pads and belts,cushions for splints, slings, and braces (for the hand, wrist, finger,forearm, knee, leg, clavicle, shoulder, foot, ankle, neck, back, rib,etc.), and also soles for orthopedic shoes. Other uses include variousshaped articles as toys, as tips for swabs, as fishing bate, as a highvacuum seal (against atmosphere pressure) which contains a useful amountof a mineral oil-based maGnetic fluid particles, etc. Moreover, thecasted, extruded, or spun threads, strips, yarns, tapes can be weavedinto cloths, fine or coarse fabrics.

The fluffy gels can be formed in any shape; the original shape can bedeformed into another shape (to contact a regular or irregular surface)by pressure and upon removal of the applied pressure, the composition inthe deformed shape will recover back to its original shape.

As an example of the versatility of use of the instant fluffy crystalgels, a hand exerciser can be made in any shape so long as it issuitable for use as a hand exerciser: a sphere shape, a cube shape, arectangular shape, etc. Likewise, a wheelchair cushion can be made fromthe composition in any shape, so long as it meets the needs of the userof the cushion. For example, a cushion can be made by forming thecomposition into a selected shape matching the contours of the specificbody part or body region. The composition can be formed into any desiredshaped, size and thickness suitable as a cushion; the shaped compositioncan be additionally surrounded with film, fabric, other foams, or anyother desired material or combinations thereof. Moreover, thecomposition can be casted onto such materials, provided such materialssubstantially maintain their integrity (shape, appearance, texture,etc.) during the casting process. The same applies for brace cushions,liners, linings and protective coverings for the hand, wrist, finger,forearm, knee, leg, and the like having highly reduce weight. The fluffygels are advantageously useful as cushions, liners, and coverings whichinterfaces the body or parts of the body with artificial devices.

Because of their improved tear resistance and resistance to fatigue, thefluffy crystal gels exhibit versatility as materials formed intohollowed thick wall body shapes for use in deep sea ice water diving orinsulating the body from extreme cold. Since the fluffy crystal gels aremore tear resistant, they are especially useful for making toys andballoons, and insulating gloves. As toy balloons, the fluffy crystalgels are safer because it will not rupture or explode when punctured aswould latex balloons which often times cause injures or death tochildren by choking from pieces of latex rubber. The fluffy crystal gelsare advantageously useful for making one layer gloves for vibrationdamping which prevents damage to blood capillaries in the fingers andhand caused by handling strong shock and vibrating equipment.

Other uses include self sealing enclosures for splicing electrical andtelephone cables and wires. For example, the fluffy crystal gels can bepre-formed into a small diameter tubing within an outer elastic tubing,both the internal fluffy crystal gel tubing and external elastic tubingcan be axially expanded and fixed in place by a removable continuousretainer. Upon insertion of a spliced pair or bundle of cables or wires,the retainer can be removed, as the retainer is removed, the fluffycrystal gel and elastic tubing impinges onto the inserted cables orwires splices, thereby sealing the electrical splices against weather,water, dirt, corrosives and shielding the splice from external abuse.The enclosure is completed without the use of heat or flame as isconventionally performed.

In all cases, the tear strength of fluffy crystal gels are higher thanthat of amorphous gels. For example, the fluffy crystal gels made fromhigh viscosity S—E—EB—S and S—E—EP—S copolymers are resistant to tearingwhen sheared than high viscosity amorphous S—EB—S and S—EP—S copolymergels. This can be demonstrated by forming a very soft gel samples, forexample 100 parts copolymer to 800 parts plasticizing oil. The soft gelis made in a 16 mm×150 mm test tube, the gel cylinder is cut or notchedat one point about its cross-section and gripped lengthwise tightly inthe left hand about this cross-section point and a length of exposed gelis gripped lengthwise around the adjacent cross-section point tightly bythe right hand as close to the left hand as possible without stretching.With the two hands gripping the gel sample's cross-section about thenotched point, the hands are moved in opposite directions to tear apartthe gel sample at the cross-section point. The shearing action by thegripping hands is done at the fastest speed possible as can be performedby human hands. Using the demonstration, the fluffy crystal gels willnot easily break or tear completely apart, whereas, amorphous S—EB—S andS—EP—S gels break or tears apart easily. Likewise the various fluffycrystal gels of the invention described herein are tested and found tobe more tear resistant than fluffy amorphous gels. For toys such asairfoils, the improved lower density and resistance to tearing areessential for acceptable performance during play.

The invention is further illustrated by means of the followingillustrative embodiments, which are given for purpose of illustrationonly and are not meant to limit the invention to the particularcomponents and amounts disclosed.

EXAMPLE I

Unexpanded methacrylonitrile microspheres #051, #053 , #091, #091-80,and #092-120 as obtained from Expandcel, In., are dispersed in Duraprime70 white oil in varying amounts to yield oil/microsphere mixtures havingthe following approximate viscosities (poise): 0.5, 0.8, 1.5, 18, 34,100, 150, 250, 400, 460, 480, 560, 720, 1000, and 2000.

EXAMPLE II

Gels of 100 parts of high viscosity linear amorphous S-EB-S (KratonG1651) block copolymer and 1,600, 1,200, 1,000, 800, 600, 500, 450, 300,250 parts by weight of Duraprime 70 while oil (plasticizer) are meltblended in an anchor mixer to obtain clear molten gels at selectedtemperatures and viscosities which are dependent on the parts by weightof oil and resultant molten viscosity (as denoted by: partsoil/temperature °F./−poise) as follows: 1,600 @275° F./−15-30 poise,1,200 @280° F./−18-25 poise, 1,000 @300° F./−20-35 poise, 800 @310°F./−30-60 poise, 600 @325° F./−50-120 poise, 500 @350° F./−100-300poise, 450 @375° F./−150-400 poise, 300 @400° F./−200-400 poise, and 250@425° F./−300-500 poise.

EXAMPLE III

Gels of 100 parts of high viscosity linear Kuraray SEPTON 2006(amorphous S-EP-S) block copolymer and 1,600 1,200, 1,000, 800, 600,500, 450, 300, 250 parts by weight of Duraprime 70 white oil(plasticizer) are melt blended in an anchor mixer to obtain clear moltengels at selected temperatures and viscosities which are dependent on theparts by weight of oil and resultant molten viscosity (as denoted by:parts oil/temperature °F./−poise) as follows: 1,600 @275° F./−15-30poise, 1,200 @280° F./−18-25 poise, 1,000 @300° F./−20-35 poise, 800@310° F./−30-60 poise, 600 @325° F./−50-120 poise, 500 @350° F./−100-300poise, 450 @375° F./−150-400 poise, 300 @400° F./−200-400 poise, and 250@425° F./−300-500 poise.

Note: As the viscosity of the oil used is increase (from Duraprime 70 to200, 300, 350, 400, etc.) so will the resultant viscosities of theoil/unexpanded thermoplastic particular mixtures and the molten gelviscosities change. As the oil viscosity is increased, the tack of thefluffy gels will increase substantially. The quantity and viscosity ofthe particulate mixtures of Examples I selected for dispersion in themolten gels of Examples II and III depends on the final fluffy geldensity desired and the molten gel viscosity and temperature as well asthe approximate amount of time necessary for adequate dispersion of theparticulate mixture in the molten gel.

EXAMPLE IV

Step 1: Determine the amounts of unexpanded particulate/oil mixtureneeded to yield the desired fluffy gel densities and match the viscosityof the mixtures of Examples I with the viscosities of the molten gels ofExamples II and III. Step 2: add additional amounts of component II asnecessary to the matched Example I mixture selected to obtain theparticulate dispersion time (mixing time) required based on thetemperature and viscosities of the molten gels of Example II and III{i.e., {fraction (1/10)}(t_(u)), ⅕(t_(u)), ⅓(t_(u)), ¼(t_(u)), ½(t_(u)),and (t_(u)), etc.,}. Step 3: while continuing heating and mixing themolten gels of Examples II and III, add the selected amounts ofunexpanded particulate/oil mixtures. Step 4: pressed, molded andextruded into various forms and shapes the resulting fluffy gels atmixing temperatures above 250° F. Step 5: allow part of the fluffy gelsto cool to room temperature and then formed it into articles byreheating the fluffy gels above 300° F. under pressure. The fluffy gelsand articles made by this procedure are found to exhibit adequateuniform dispersion of the expanded microspheres for densities of about0.7 g/cm³, 0.65 g/cm³, 0.60 g/cm³, 0.55 g/cm³, 0.50 g/cm³, 0.45 g/cm³,0.40 g/cm³, 0.35 g/cm³, 0.30 g/cm³, and 0.28 g/cm³. The fluffy gels arefound to exhibit gel rigidities of from about 20 to about 3,000 gramBloom, and elongations of at least 200%.

EXAMPLE V

Procedures of Example IV is repeated using high viscosity crystallinemidblock segment linear S-E-EB-S and (S-E-EB)_(n) multi-arm blockcopolymers (n=2, 3, 4, and 5) with ethylene to ethylene/butylenemidblock ratios (E:EB) of 89:11, 88:12, 87:13, 86:14, 85:15, 84:16,83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26,73:27, 72:28, 71:29, and 70:30. It is found the procedure of the Exampleis capable of producing fluffy gels of about 0.6 g/cm³ to about 0.30g/cm³, gel rigidities of from about 20 to about 3,000 gram Bloom,elongations of at least 200%, and the tensile strength, notched tearstrength, and resistance to fatigue are found to be greater than that offluffy amorphous gels of Examples IV.

EXAMPLE VI

Procedures of Example IV is repeated using high viscosity crystallinemidblock segment linear S-E-EP-S and radial (S-E-EP)_(n) multi-arm blockcopolymers. It is found the procedure of the Example is capable ofproducing fluffy gels of about 0.6 g/cm³ to about 0.30 g/cm³, gelrigidities of from about 20 to about 3,000 gram Bloom, elongations of atleast 200%, and the tensile strength, notched tear strength, andresistance to fatigue are found to be greater than that of fluffyamorphous gels of Examples IV.

EXAMPLE VII

Procedures of Example IV is repeated using high viscosity crystallinemidblock segment linear (S-B-S), (S-B-EP-S), (S-B-EB-S), (S-B-EP-B-S),(S-B-EB-B-S), (S-B-EB-EP-S), (S-B-EP-EB-S), (S-EB-EP-S), (S-EP-B-EP-S),(S-B-EB-B-EB-S), (S-B-EB-B-EP-S), and (S-B-EP-B-EP-B-S) blockcopolymers. It is found the procedure of the Example is capable ofproducing fluffy gels of about 0.6 g/cm³ to about 0.03 g/cm³, gelrigidities of from about 20 to about 3,000 gram Bloom, elongations of atleast 200%, and the tensile strength, notched tear strength, andresistance to fatigue are found to be lower than that of fluffy crystalgels of Examples V and VI.

EXAMPLE VIII

Example IV is repeated using high viscosity crystalline midblock segmentlinear (S-E-EB₂₅-S), (S-EP-E-EP-S), (S-E-EB-S), (S-E-EP-S),(S-E-EP-E-S), (S-E-EB-B-S), (S-E-B-EB-S), (S-E-B-EP-S), (S-E-EB-EP-S),(S-E-EP-EB-S), (S-E-EP-E-EP-S), (S-E-EP-E-EB-S), (S-E-EB-B-EP-S),(S-E-EP-B-EB-S), (S-E-EP-E-EP-E-S), (S-E-EP-E-EB-S), (S-E-EP-E-EP-EB-S),(S-E-EP-E-EP-E-S), and (S-E-EP-EB-EP-EB-B-S) block copolymers. It isfound the procedure of the Example is capable of producing fluffy gelsof about 0.6 g/cm³ to about 0.30 g/cm³, gel rigidities of from about 20to about 3,000 gram Bloom, elongations of at least 200%, and the tensilestrength, notched tear strength, and resistance to fatigue are found tobe greater than that of amorphous gels of Example IV.

EXAMPLE IX

Example IV is repeated using high viscosity polyurethane elastomersformed from a hydroxyl terminated poly(ethylene-butylene) oligomerhaving TMP/diisocyanate and BEPD/diisocyanate copolymer crystallinegroups. The fluffy polyurethane elastomer gels are formed at betweenabout 375° C. to about 450° C. It is found the procedure of the Exampleis capable of producing fluffy gels of about 0.6 g/cm³ to about 0.30g/cm³, gel rigidities of from about 20 to about 3,000 gram Bloom,elongations of at least about 200%, and the tensile strength, notchedtear strength, and resistance to fatigue are found to be greater thanthat of amorphous gels of Example IV.

EXAMPLE X

Example IV is repeated using high viscosity crystalline midblock segmentmultiarm (S-E-EB)_(n), (S-E-EP)_(n), (S-E-EP-E)_(n), (S-E-EB-B)_(n),S-E-B-EB)_(n), (S-E-B-EP)_(n), (S-E-EB-EP)_(n), (S-E-EP-EB)_(n),(S-E-EP-E-EP)_(n), (S-E-EP-E-EB)_(n), (S-E-EB-B-EP)_(n),(S-E-EP-B-EB)_(n), (S-E-EP-E-EP-E)_(n), (S-E-EP-E-EB)_(n),(S-E-EP-E-EP-EB)_(n), (S-E-EP-E-EP-E)_(n), and (S-E-EP-EB-EP-EB-B)_(n),with n=2, 3, 4, and 5 block copolymers. It is found the procedure of theExample is capable of producing fluffy gels of about 0.6 g/cm³ to about0.30 g/cm³, gel rigidities of from about 20 to about 3,000 gram Bloom,elongations of at least 200%, and the tensile strength, notched tearstrength, and resistance to fatigue are found to be greater than that ofamorphous gels of Example IV.

EXAMPLE XI

Examples IV, V, VI, VII and VIII are repeated with the addition of 2, 5,and 10 parts by weight of ethylene-butyl acrylate, ethylene-ethylacrylate, ethylene-methyl acrylate, ethylene-vinyl acetate,acrylonitrile-styrene-acrylate, styrene-acrylonitrile, styrene-maleicanhydride, meleated poly(styrene-ethylene-propylene-styrene) andmeleated poly(styrene-ethylene-butylene-styrene). It is found theprocedure of the Examples is capable of producing fluffy gels of about0.6 g/cm³ to about 0.30 g/cm³, gel rigidities of from about 20 to about3,000 gram Bloom, elongations of at least 200% and when the fluffy gelsare formed with various substrates, such as fabric, the shedding ofexpanded microspheres at the fluffy gel and fabric interface at thetests areas of fatigue failure appears to be reduced.

EXAMPLE XII

Example IX is repeated using high viscosity polyurethane elastomersformed from hydroxyl terminated poly(ethylene-propylene),poly(ethylene-ethylene/butylene), poly(ethylene-ethylene/propylene), andpoly(butylene) oligomers having TMP/diisocyanate and BEPD/diisocyanatecopolymer crystalline groups. The fluffy polyurethane elastomer gels areformed at between about 375° C. to about 450° C. It is found theprocedure of the Example is capable of producing fluffy gels of about0.6 g/cm³ to about 0.03 g/cm³, gel rigidities of from about 20 to about3,000 gram Bloom, elongations of at least 200%, and the tensilestrength, notched tear strength, and resistance to fatigue are found tobe greater than that of fluffy amorphous gels of Example IV.

EXAMPLE XIII

Examples IV, V, VI, VII and VIII are repeated with the addition of 2, 5,and 10 parts by weight of Dowlex 3010, 2077, Dow Affinity ethylenealpha-olefin resin PL-1840, SE-1400, SM-1300, Dow Elite 5100, 5200,5400, Dow Attane (ultra low density ethylene-octene-1copolymers) 4803,and 4602. It is found the procedure of the Examples is capable ofproducing fluffy gels of about 0.6 g/cm³ to about 0.03 g/cm³, gelrigidities of from about 20 to about 3,000 gram Bloom, elongations of atleast 200% and the tear and rupture resistance of the fluffy gelscontaining the polyolefins appear to improve over the fluffy gels absentsuch polyolefins.

While preferred components and formulation ranges have been disclosedherein persons of skill in the art can extend these ranges usingappropriate material according to the principles discussed herein.Furthermore, Crystalline midblock segment block polymers can be use inblending with other engineering plastics and elastomeric polymers tomake alloyed compositions having improved impact and tear resistanceproperties. All such variations and deviations which rely on theteachings through which the present invention has advanced the art areconsidered to be within the spirit and scope of the present inventionand it is not intended to limit the invention to the exact details shownabove except insofar as they are defined in the following claims.

What I claim is:
 1. A cold weather wear for protecting parts of a bodyagainst cold comprising: a footwear, a sock, a face mask, a glove and abody suit for protection of one or more selected areas of said bodyincluding the head, face, forehead, eyes, ears, nose, neck, hand,fingers, arms, underarm, torso, and back; said cold weather wear madefrom (I) one or more layers of a crystal gel, G_(n), comprising: (i) 100parts by weight of at least one or more a linear, multi-arm, branched,or star shaped block copolymer or a mixture thereof, said blockcopolymer having one or more substantially crystalline poly(ethylene)midblock in combination with one or more amorphous midblocks ofpoly(butylene), poly(ethylene-butylene), poly(ethylene-propylene) or acombination thereof, (ii) about 300 to about 1,600 parts by weight of aplasticizing oil; in combination with or without (II) at least one layerof an insulating gel formed from said (i) crystal gel, G_(n), incombination with (iii) a selected amount of one or more heat expandableplastic or synthetic particulates of material so as to form ahomogeneous or non-homogeneous closed cell particulate gel dispersion,G_(n)M_(m), wherein said crystal gel G_(n) having a gel rigidity of fromabout 20 to about 1,000 gram Bloom, said gel dispersion, G_(n)M_(m),having a gel rigidity of from 50 to about 3,000 gram Bloom, said crystalgel, Gn, and said gel dispersion, G_(n)M_(m), having an elongation of atleast 200%, said crystal gel or crystal gel dispersion, G_(n)M_(m),capable of being formed in adhering contact with each other, anothercrystal gel dispersion or physically interlocked with a selectedsubstrate material, M_(n), to form one or more combinations of a crystalgel-substrate, crystal gel dispersion substrate, or crystalgel-substrate/crystal gel dispersion composites including anon-composite of a crystal gel dispersion alone, or a sequentialaddition or permutation of said combinations of (G_(n)M_(m)),(G_(n)M_(m))(G_(n)M_(m)), (G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m)),M_(n)M_(n)(G_(n)M_(m)), M_(n)G_(n)G_(n)(G_(n)M_(m)),M_(n)M_(n)M_(n)(G_(n)M_(m)), including M_(n)G_(n)(G_(n)M_(m)),(G_(n)M_(m))G_(n)M_(n), G_(n)(G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m))M_(n),M_(n)(G_(n)M_(m))G_(n), (G_(n)M_(m))G_(n)G_(n), (G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)M_(n), (G_(n)M_(m))G_(n)M_(n)M_(n),(G_(n)M_(m))G_(n)M_(n)G_(n), (G_(n)M_(m))M_(n)G_(n)G_(n),G_(n)G_(n)(G_(n)M_(m))M_(n), M_(n)G_(n)(G_(n)M_(m))G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m)), G_(n)(G_(n)M_(m))M_(n)M_(n),(G_(n)M_(m))M_(n)(G_(n)M_(m)), G_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n), G_(n)(G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m)),(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)),G_(n)(G_(n)M_(m))M_(n)G_(n)G_(n), M_(n)M_(n)G_(n)(G_(n)M_(m))M_(n),M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), (G_(n)M_(m))(G_(n)M_(m))G_(n),M_(n)M_(n)M_(n)(G_(n)M_(m))M_(n)M_(n),M_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),M_(n)(G_(n)M_(m))(G_(n)M_(m))M_(n)G_(n),(G_(n)M_(m))M_(n)(G_(n)M_(m))M_(n)G_(n),M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m))M_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(n)),(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n)G_(n), or(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n), where when n is asubscript of G, n denotes the same or different gel rigidity; were whenn is a subscript of M, n denotes the same or different material of foam,plastic, fabric, knit fabric, yarn knit fabric, metal, wood, glassfiber, ceramics, synthetic resin, synthetic fibers or refractorymaterials; where when m is the subscript of M, m denotes the same ordifferent microsphere of glass or thermoplastic resin; said compositesformed of one or more crystal gels or crystal gel dispersion of the sameor different gel rigidity and one or more substrates of the same ordifferent material; said crystal gel or crystal gel dispersion formedwith or without (iv) one or more of a selected polar polymer and incombination with or without (v) one or more of a selected crystalline ornon-crystalline polymer or copolymer.
 2. A cold weather sock forfootwear formed of a gel composite of claim 1, for direct contact withthe foot and capable of substantially preventing the generation moisturefrom said foot.
 3. A cold weather footwear having an outer boot, aperformed sock disposed in said boot and formed of a gel compositeaccording to claim 1 for direct contact with the foot and capable ofsubstantially preventing the generation moisture from said foot.
 4. Acold weather face mask for protection of the head, face, and neck areasagainst low temperatures and high wind velocities made from the gelcomposite of claim 1 for direct contact with the head, face, and neckand capable of substantially preventing the generation moisture fromsaid head, face, and neck and having openings for insertion and removalof one or more hydrophilic patches in selected area covered by saidmask.
 5. A cold weather sock, face mask, and body suit for protection ofthe body areas including the head, face, hand, fingers, nose, ears,neck, torso, back, arms, and foot against low temperatures and high windvelocities made from the gel composite of claim 1 for direct contactwith the body and capable of substantially preventing the generationmoisture from said body and having openings for insertion and removal ofone or more hydrophilic patches in selected areas of the body covered bysaid suit.
 6. A cold weather wear according to claim 1, wherein said (i)block copolymer is poly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-propylene-styrene),poly(styrene-ethylene-styrene), poly(styrene-butylene-styrene),poly(styrene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/butylene-sytrene),poly(styrene-ehtylene-ethylene/propylene-ethylene-styrene),poly(styrene-ethylene-ethylene/butylene-butylene-styrene),poly(styrene-butylene-ethylene/propylene-butylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-styrene),poly(styrene-ethylene-butylene-ethylene/butylene-styrene),poly(styrene-ethylene-butylene-ethylene/propylene-styrene), poly(styreneethylene/butylene-ethylene/propylene-styrene), poly(styreneethylene-ethylene/butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-butylene-ethylene/butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene/propylene-butylene-ethylene/propylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene-styrene),poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/butylene-butylene-ethylene/propylene-styrene),poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene-sytrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene),poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene-styrene),poly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylene-butylene-styrene),poly(styrene-ethylene-butylene)n, poly(styrene-ethylene-propylene)n,poly(styrene-ethylene)n, poly(styrene-butylene)n,poly(styrene-ethylene-ethylene/butylene)n,poly(styrene-ethylene-ethylene/propylene)n,poly(styrene-butylene-ethylene/propylene)n,poly(styrene-butylene-ethylene/butylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene)n,poly(styrene-ethylene-ethylene/butylene-butylene)n,poly(styrene-butylene-ethylene/propylene-butylene)n,poly(styrene-butylene-ethylene/butylene-butylene)n,poly(styrene-ethylene-butylene-ethylene/butylene)n,poly(styrene-ethylene-butylene-ethylene/propylene)n,poly(styrene-ethylene/butylene-ethylene/propylene)n,poly(styrene-ethylene-ethylene/butylene-ethylene/propylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene/butylene)n,poly(styrene-butylene-ethylene/butylene-ethylene/propylene)n,poly(styrene-butylene-ethylene/propylene-ethylene/butylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)n,poly(styrene-ethylene/propylene-butylene-ethylene/propylene)n,poly(styrene-butylene-ethylene/butylene-butylene-ethylene/butylene)n,poly(styrene-butylene-ethylene/butylene-butylene-ethylene/propylene)n,poly(styrene-ethylene-ethylene/butylene-butylene-ethylene/propylene)n,poly(styrene-ethylene-ethylene/propylene-butylene-ethylene/butylene)n,poly(styrene-ethylene-ehtylene/propylene-ethylene-ethylene/propylene-ethylene)n,poly(styrene-butylene-ethylene/propylene-butylene-ethylene/propylene-butylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/butylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene/butylene)n,poly(styrene-ethylene-ethylene/propylene-ethylene-ethylene/propylene-ethylene)n,orpoly(styrene-ethylene-ethylene/propylene-ethylene/butylene-ethylene/propylene-ethylene/butylene-butylene)nor a mixture thereof.
 7. A cold weather wear according to claim 1,wherein said (iv) polar polymer is ethylene-butyl acrylate,ethylene-ethyl acrylate, ethylene-methyl acrylate, ethylene-vinylacetate, ethylene-vinyl acrylate, ethylene vinyl alcohol, acrylonitrilestyrene-acrylate, styrene-acrylonitrile, styrene-maleic anhydride,meleated poly(styrene-ethylene-propylene-styrene), meleatedpoly(styrene-ethylene-butylene-styrene) or a mixture thereof.
 8. A coldweather wear according to claim 1, wherein said selected (v) crystallineor non-crystalline polymer or copolymer ispoly(styrene-butadiene-styrene), poly(styrene-butadiene),poly(styrene-isoprene-styrene), poly(styrene-isoprene),poly(styrene-ethylene-propylene), low viscositypoly(styrene-ethylene-propylene-styrene), low viscositypoly(styrene-ethylene-butylene-styrene),poly(styrene-ethylene-butylene), meleatedpoly(styrene-ethylene-butylene-styrene), high vinyl contentpoly(styrene-ethylene-butylene-styrene), poly(styrene-ethylenepropylene-styrene-ethylene-propylene), poly(ethylene-propylene),poly(styrene-butadiene)n, poly(styrene-butadiene)n, poly(styreneisoprene)n, poly(styrene-isoprene)n, poly(styrene-ehtylene propylene)n,low viscosity poly(styrene-ethylene-propylene)n, low viscositypoly(styrene-ethylene-butylene), poly(styrene-ethylene-butylene)n,meleated poly(styrene-ethylene-butylene)n, high vinyl contentpoly(styrene-ethylene-butylene)n, poly(styrene-ethylenepropylene-styrene-ethylene-propylene)n, poly(ethylene-propylene)n,polystyrene, polybutylene, poly(ethylene-propylene),poly(ethylene-butylene), polypropylene, polyethylene, polypthalamide orpolyurethane elastomer formed from one or more saturated hydrocarbondiols, wherein said selected block copolymer is a linear, branched,multiarm, or star shaped copolymer.
 9. A cold weather wear according toclaim 1, wherein said (i) copolymer of said gel is a thermoplasticpolyurethane elastomer made with diisocyanates and chain extenders 2,2,4trimethyl-1,3-pentancdiol or 2 Butyl-2-ethyl-1,3-pentanediol and asaturated hydrocarbon diol, said polyurethane having one or morecrystalline groups of about 22% to about 45% wy weight of said elastomerand capable of exhibiting a glass transition of at least about −40° C.10. A cold weather wear according to claim 9, wherein said hydrocarbondiols is a hydroxyl terminated oligomer of poly(ethylene-butylene) orpoly(ethylene-propylene).
 11. A cold weather sock for footwear formed ofa gel composite of claim 1, for direct contact with the foot and capableof substantially preventing the generation moisture from said foot. 12.A cold weather footwear according to claim 1 comprising: (a) an outerboot, (b) a performed sock disposed in said boot, said sock being amulti-interwoven layer sock disposed in said boot, said multi-interwovenlayer having one or more inner top interwoven layers impregnated withsufficient amounts of said crystal gel so as to form a stable supportand sufficient for encapsulating and sealing the skin of the foot fromair and prevent the production of foot moisture.
 13. A cold weatherfootwear according to claim 1 comprising: (a) an outer boot, (b) ahighly stable boot inner support having a top portion and a bottom innerinsulating support portion , said top inner support portion having a fewmillimeter of surface made from a natural or synthetic dense battingmaterial, said bottom inner insulating support portion having a denseopen cell foam, or a felt material; said bottom insulating inner supportportion forming a support for an inner gel sock disposed within saidinner support, said inner gel sock being impregnated with sufficient gelso as to form a highly stable support and capable of encapsulating andsealing the skin of the foot from air and prevent the production of footmoisture; said inner gel sock having an outer polymeric membrane or filmfor separating said gel sock from said inner support to preventmigration of said gel or said plasticizing oil into said inner supportor said bottom inner insulating support portion.
 14. A cold weather facemask according to claim 1, for protection of said head, face, eye, andneck areas against low temperature and high wind velocities being madefrom the crystal gel or crystal gel composite for direct contact withthe head, face, and neck having openings for insertion and removal ofone or more hydrophilic patches in selected areas covered by said mask,said eye area with or without a corrective lens or wide view visor beingincorporated with a visor tri-layers of M_(n)G_(n)M_(n) orG_(n)M_(n)G_(n), said visor tri-layers including a polystyrene layer/gellayer/polystyrene layer, a polycarbonate layer/gel layer/polycarbonatelayer, a crystalline polypropylene layer/gel layer/polypropylene layer,or a clear silicon layer/gel layer/silicone layer; said hydrophilicpatches being held in place by said gel on one side and in directcontact with the skin, held in place in a slit pocket between said gel,or held in place in a foam pocket or fabric pocket layer facing theskin); said hyrophilic patches comprising a natural materials, a waterabsorbing polymer, a hydrogel forming polymer, a salt tolerant superabsorbent, a starch modified absorbent or a polysaccharide, a starch ora cellulose modified polymer.
 15. A cold weather wear for protectingparts of a body against cold comprising: a footwear, a sock, a facemask, a glove and a body suit for protection of one or more selectedareas of said body including the head, face, forehead, eyes, ears, nose,neck, hand, fingers, arms, underarm, torso, and back; said cold weatherwear made from (I) one or more layers of a crystal gel, G_(n),comprising: (i) 100 parts by weight of at least one linear, multi armbranched, or star shaped block copolymer or a mixture thereof, saidblock copolymer having one or more substantially crystallinepoly(ethylene) midblock in combination with one or more amorphousmidblocks or poly(butylene), poly(ethylene-butylene),poly(ethylene-propylene) or a combination thereof, (ii) about 300 toabout 1,600 parts by weight of a plasticizing oil; (II) one or morelayers of an insulating crystal gel, (G_(n)M_(m)), comprising: (iii) agel dispersion of said crystal gel, G_(n), and a selected amount of oneor more heat expandable plastic or synthetic particulates of material,M_(m), so as to form a homogeneous or non-homogeneous closed cellparticulate gel dispersion (G_(n)M_(m)), where when m is the subscriptof M, m denotes the same or different microsphere of glass ofthermoplastic resin; (III) a combination of said crystal gel or acrystal gel composite, G_(n)M_(n) or G_(n)G_(n), with one or more layersof said insulating crystal gel; said crystal gel composite comprising:G_(n) in adhering contact, laminated or physically interlocked with aselected material M_(n) to form said crystal gel composite comprisingcombinations of G_(n) and M_(n) or G_(n) and G_(n) any sequentialadditions or permutations of said combinations G_(n)G_(n), M_(n)G_(n),G_(n)M_(n)G_(n), M_(n)G_(n)M_(n), M_(n)G_(n)G_(n), M_(n)M_(n)G_(n),M_(n)GnG_(n)G_(n), M_(n)M_(n)M_(n)G_(n), including M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n), G_(n)G_(n)M_(n)G_(n), M_(n)G_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n), G_(n)M_(n)G_(n)G_(n), G_(n)M_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n), G_(n)G_(n)M_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)M_(n), G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n)G_(n), G_(n)G_(n)G_(n)M_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n), M_(n)G_(n)M_(n)G_(n)M_(n),G_(n)G_(n)M_(n)M_(n)M_(n), G_(n)M_(n)M_(n)G_(n)M_(n),G_(n)G_(n)G_(n)M_(n)G_(n)G_(n), M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)M_(n)G_(n), G_(n)G_(n)M_(n)G_(n)M_(n)G_(n),G_(n)M_(n)G_(n)M_(n)G_(n)M_(n), G_(n)M_(n)M_(n)G_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n)M_(n), G_(n)G_(n)M_(n)M_(n)G_(n)G_(n),M_(n)M_(n)G_(n)G_(n)M_(n)M_(n), M_(n)G_(n)G_(n)M_(n)G_(n)M_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n), G_(n)G_(n)M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)G_(n), M_(n)M_(n)M_(n)G_(n)M_(n)M_(n)M_(n),M_(n)G_(n)M_(n)G_(n)G_(n)M_(n), G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),M_(n)G_(n)M_(n)G_(n)M_(n)M_(n)G_(n),G_(n)M_(n)M_(n)G_(n)M_(n)M_(n)G_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n),G_(n)G_(n)M_(n)M_(n)G_(n)G_(n)M_(n)M_(n),G_(n)G_(n)M_(n)G_(n)G_(n)M_(n)G_(n)G_(n),M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n),G_(n)M_(n)G_(n)G_(n)M_(n)G_(n)G_(n)M_(n)G_(n),G_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)G_(n), orG_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n)G_(n)G_(n)M_(n)G_(n)M_(n)G_(n)M_(n)G_(n),where when n is a subscript of G, n denotes the same or different gelrigidity; where when n is a subscript of M, n denotes the same ordifferent material of foam, plastic, fabric, knit fabric, yarn knitfabric, metal, wood, glass fiber, ceramics, synthetic resin, syntheticfibers or refractory materials; said insulating gel capable of beingmade in adhering contact, laminated or physically interlocked with saidcrystal gel or said crystal gel composite, or another gel dispersion orphysically interlocked with a selected substrate material, M_(n), toform one or more combinations of a crystal gel-gel dispersion, geldispersion-substrate, or crystal gel substrate/gel dispersion compositesincluding a non composite of a gel dispersion alone, or a sequentialaddition or permutation of said combinations of (G_(n)M_(m)),(G_(n)M_(m))(G_(n)M_(m)), (G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m)),M_(n)M_(n)(G_(n)M_(m)), M_(n)G_(n)G_(n)(G_(n)M_(m)),M_(n)M_(n)M_(n)(G_(n)M_(m)), including M_(n)G_(n)(G_(n)M_(m)),(G_(n)M_(m))G_(n)M_(n), G_(n)(G_(n)M_(m))G_(n), M_(n)(G_(n)M_(m))M_(n),M_(n)(G_(n)M_(m))G_(n), (G_(n)M_(m))G_(n)G_(n), (G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)M_(n), (G_(n)M_(m))G_(n)M_(n)M_(n),(G_(n)M_(m))G_(n)MnG_(n), (G_(n)M_(m))M_(n)G_(n)G_(n),G_(n)G_(n)(G_(n)M_(m))M_(n), M_(n)G_(n)(G_(n)M_(m))G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m)), G_(n)(G_(n)M_(m))M_(n)M_(n),(G_(n)M_(m))M_(n)(G_(n)M_(m)), G_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),M_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n), G_(n)(G_(n)M_(m))M_(n)G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m)),(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)),G_(n)(G_(n)M_(m))M_(n)G_(n)G_(n), M_(n)M_(n)G_(n)(G_(n)M_(m))M_(n),M_(n)G_(n)(G_(n)M_(m))(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))G_(n)G_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), (G_(n)M_(m))(G_(n)M_(m))G_(n),M_(n)M_(n)M_(n)(G_(n)M_(m))M_(n)M_(n),M_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), M_(n)(G_(n)M_(m))(G_(n)M_(m))M_(n)G_(n), (G_(n)M_(m))M_(n)(G_(n)M_(m))M_(n)G_(n),M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), M_(n)G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m)), (G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))M_(n)G_(n)(G_(n)M_(m))M_(n),G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)G_(n),(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m)),(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n)(G_(n)M_(m))G_(n),G_(n)(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n)G_(n), or(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))(G_(n)M_(m))G_(n); saidcrystal gel composites formed of one or more crystal gels or geldispersion of the same or different gel rigidity and one or moresubstrates of the same or different material; said crystal gel having agel rigidity of from about 20 to about 1,000 gram bloom, said geldispersion, (G_(n)M_(m)), having a gel rigidity of from 50 to about3,000 gram Bloom, said crystal gel and said insulating gel having anelongation of at least 200%; said crystal gel or gel dispersion formedwith or without (iv) one or more of a selected polar polymer and incombination with or without (v) one or more of a selected crystalline ornon-crystalline polymer or copolymer; (vi) said crystal gel beingapplied with or without one or more antiperspirant agents, deodorantagents, antibacterial agents, antifungal agents, or hydrophobic agents,or a combination of said agents.